Reinforcement of model filled elastomers: characterization of the cross-linking density at the filler-elastomer interface by H NMR measurements

The cross-linking density at the filler-elastomer interface is analyzed by ¹H NMR measurements in model reinforced elastomers composed by grafted nanosilica particles and cross-linked ethylacrylate chains. We have focused our attention on the effect of introducing fillers on the relaxation of the bulk polymer matrix which is observed at long times (t>100 μs). Measurements performed at high temperature (T>T_g+120 K) have revealed that its relaxation is affected by the topological constraints existing at the particle surface. We deduce that the effect of particles in the bulk matrix can be interpreted as that of an homogeneous additional constraint density which increases proportionally to the surface area introduced in the matrix.     

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.     

Pulsed n.m.r. studies of molecular motion in wet nylon-6,6 fibres

The influence of water molecules on molecular motion in commercial nylon-6,6 fibres has been investigated by pulsed n.m.r. techniques. Transient n.m.r. signals, T₂ and T₁ relaxation times for the fibre protons were measured as a function of temperature and moisture (D₂O) content. Above the glass transition temperature, T_g, of the fibre, separation of the signal into two components, a ‘rigid’ and ‘non-rigid’ fraction, was possible. For wet fibres, the temperature at which the ‘non-rigid’ or ‘mobile’ component appeared was reduced as the water content was increased and the ‘mobile fraction’ increased with temperature. This behaviour is explained in terms of the mobilization of amorphous chain segments above the T_g and their ability to be ‘plasticized’ by water molecules. The effect of D₂O molecules and paramagnetic Mn²⁺ ions on T₁ relaxation of rigid and mobile segments provided further information on the properties of accessible chain segments between and on the crystallite surfaces. A chain folded model of semi-crystalline morphology has been adopted throughout the discussion.     

Solid polymer electrolytes VIII: effect of LiClO4-doped level on the microstructure and ionic conductivity of a chemical-covalently polyether-siloxane hybrid electrolyte

A new hybrid polymer electrolyte system based on chemical-covalently polyether and siloxane phases is designed and prepared in the presence of lithium perchlorate (LiClO₄) which acted as both ionic source and the epoxide ring-opening catalyst. The effect of salt-doped level on the microstructure and ionic conductivity of these composite electrolytes were investigated by means of Fourier transform infra-red spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, a.c. impedance and multinuclear solid-state nuclear magnetic resonance measurements. DSC results indicate that the formation of transient cross-links between Li⁺ ions and the ether oxygens on complexation with LiClO₄ results in an increase in polyether segment T_g. However, the polyether segment T_g decreases at the highest salt concentration (5.0 mmol LiClO₄/g PEGDE), ascribing to the plasticizing effect. The behavior of ion transport is coupled with the segmental motions of polymer chains and also correlated with the interactions between ions and polymer host.     

The effect of the dry glass transition temperature on the synthesis of paraffin microcapsules obtained by suspension‐like polymerization

PRS® paraffin wax was encapsulated by means of suspension‐like copolymerization of methyl methacrylate (MMA) with butyl acrylate (BA). The effects of the polymeric shell dry glass transition temperature (T_g) and the reaction temperature (T_r) were then studied. Additionally, the evolution of particle diameter, molecular weight, conversion, and T_g during polymerization was also researched. The chemical properties of the shell material (acrylic polymer), together with those found in the core material (PRS® paraffin wax), for instance: polarity and interfacial tensions, largely determine whether the morphology of the microcapsules will be thermodynamically favored or not. The high polarity of MMA (γ₀ = 18 mN m^?1) and BA (γ₀ = 24 mN m^?1) should provide a thermodynamic driving force to cover the paraffin wax droplet which would result in a core/shell thermodynamically favored structure. However, most systems are defined by kinetics rather than thermodynamics such as the monomers dry T_g and T_r. It was observed that penetration of polymer radical chains was severely limited when the dry T_g was ≥10°C above the reaction temperature, resulting in irregular and undifferentiated particles. However, penetration did occur when the copolymeric shell dry T_g was ～10°C below the reaction temperature which led to uniform and spherical particles being synthesized. POLYM. ENG. SCI., 54:208–214, 2014. © 2013 Society of Plastics Engineers     

A study on polymer blend electrolyte based on PVA/PVP with proton salt

Proton-conducting polymer blend electrolytes based on PVA–PVP–NH₄NO₃ were prepared for different compositions by solution cast technique. The prepared films are investigated by different techniques. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR and laser Raman studies confirm the complex formation between the polymer and salt. DSC measurements show decrease in T _g with increasing salt concentration. The ionic conductivity of the prepared polymer electrolyte was found by ac impedance spectroscopy analysis. The maximum ionic conductivity was found to be 1.41 × 10^?3 S cm^?1 at ambient temperature for the composition of 50PVA:50PVP:30 wt% NH₄NO₃ with low-activation energy 0.29 eV. The conductivity temperature plots are found to follow an Arrhenius nature. The dielectric behavior was analyzed using dielectric permittivity (ε*) and the relaxation frequency (τ) was calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer blend electrolyte, the primary proton battery with configuration Zn + ZnSO₄·7H₂O/50PVA:50PVP:30 wt% NH₄NO₃/PbO₂ + V₂O₅ was fabricated and their discharge characteristics studied.     

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.     

Mixing effects on the mid-kilohertz mobility of polystyrene in glassy polystyrene-diluent blends

Low molecular weight additive effects on the mid-kilohertz mobility of atactic polystyrene (PS) at 25°C via n.m.r. spin-lattice relaxation experiments in the rotating frame (T_1?) are analogous to the results of a previous study of diluents in glassy bisphenol-A polycarbonate. The diluent with a relatively low glass transition temperature (T_g), dioctylphthalate, increases the spectral density of thermal motions of the chain backbone and the pendant group in PS on the order of 38.5 kHz. Of the ¹³C nuclei in the glassy polymer, the relaxation behaviour of which can be differentiated by high-resolution, solid-state n.m.r., the T_1?'s of the aromatic carbons in the side group are affected most by dioctylphthalate. In contrast, the styrene oligomer, which has a higher T_g than that of dioctylphthalate, does not significantly alter the ambient temperature mobility of polystyrene at 38.5 kHz. The PS-styrene oligomer and PS-dioctylphthalate blends are examples of athermal and non-athermal mixtures, respectively. However, the effect of the enthalpy of mixing on the T_1?'s of the polymer is probably obscured by differences in blend mobility due to different blend T_g's.     

Change of the amorphous state by heat treatment below the glass transition temperature

This study was undertaken to elucidate the state of a polymer in the amorphous state through a change of motion of the molecular chain caused by heat treatment below the glass transition temperature. From dielectric measurements of amorphous poly(ethylene terephthalate) heat-treated below T_g, it was found that the average relaxation time, the distribution of relaxation time and the dielectric strength increase with increase of heat treatment. From these results, it was concluded that the amorphous state becomes more random by heat treatment.     

Studies on the preparation of stable and high solid content emulsifier‐free latexes and characterization of the obtained copolymers for MMA/BA system with the addition of AHPS

3‐Allyloxy‐2‐hydroxyl‐propanesulfonic (AHPS) salt was synthesized and used as a hydrophilic comonomer for the methyl methacrylate (MMA) and n‐butyl acrylate (BA) emulsifier‐free emulsion copolymerization system to obtain latices of stable and high‐solid content. Properties of the latices, such as flow behavior, stability, and final diameter of the latex particles were studied. In addition, physical properties of the obtained copolymers, such as glass transition temperature (T_g), stress–strain behavior, and water resistance were investigated. With the addition of AHPS, the latices of stable and high‐solid content (as high as 60%) were prepared. Flow of the latices follows the law of the Bingham body. The final diameter of the latex particles is 0.3–0.5 μm in diameter, which is larger than that of the conventional latex particles and decreases with the increase of AHPS and potassium persulfate (KPS) concentration. All the copolymers are atactic polymers, showed as single T_g on dynamic mechanical analysis spectrum. Compared with the copolymers that were prepared by surfactant emulsion polymerization, tensile strength, as well as water resistance is greatly improved. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 21–28, 2001     

NMR studies of thermo-responsive behavior of an amphiphilic poly(asparagine) derivative in water

The thermo-responsive behavior of a unique biocompatible polymer, poly(N-substituted α/β-asparagine) derivative (PAD), has been studied with several NMR methods. The ¹H and ¹³C solution NMR measurements of the PAD in DMSO-d₆ were used to investigate the isolated polymer and perform spectral assignments. By systematic addition of D₂O we have tracked structural changes due to aggregation and observed contraction of hydrophilic side chains. Solution and cross polarization/magic angle spinning (CP/MAS) ¹³C NMR approaches were implemented to investigate the aggregates of the PAD aqueous solution during the liquid to gel transition as the temperature was increased. At temperatures near 20 °C, all of the peaks from the PAD were observed in the ¹³C CP/MAS and ¹³C solution NMR spectra, indicating the presence of polymer chain nodes. Increasing the temperature to 40 °C resulted in a partial disentanglement of the nodes due to thermal agitation and further heating resulted in little to no additional structural changes. Deuterium T₁–T₂ and T₂–T₂ two-dimensional relaxation spectroscopies using an inverse Laplace transform, were also implemented to monitor the water–PAD interaction during the phase transition. At temperatures near 20 °C the dynamical characteristics of water were manifested into one peak in the deuterium T₁–T₂ map. Increasing the temperature to 40 °C resulted in several distinguishable reservoirs of water with different dynamical characteristics. The observation of several reservoirs of water at the temperature of gel formation at 40 °C is consistent with a physical picture of a gel involving a network of interconnected polymer chains trapping a fluid. Further increase in temperature to 70 °C resulted in two non-exchanging water reservoirs probed by deuterium T₂–T₂ measurements.     

Conformational effects on glass transition temperature and relaxation phenomena of polymers

The glass transition temperature, T_g, of a polymer has been defined as the temperature at which the segmental motions of molecular chains in the quasiequilibrium glassy state overcome the intermolecular attractions. As the thermodynamic criterion of T_g, both of the conditions ΔF = 0 and ?f_r = f^v_r should be accepted, where f_r and f^v_r are the conformational free energy and the intermolecular cohesive free energy per structural unit, respectively, and ΔF the free energy difference per molar chain between the frozen solid part and the flow part, still unfrozen at a given temperature in the vicinity of T_g. The equation for T_g has been derived by use of the criterion for T_g in the present work. The conformational effect on relaxation phenomena (the WLF equation) in polymers has been thermodynamically examined by use of the partition function taking into account both the conformational character of the polymer and the free volume for the polymer liquid. The constant C′₂ in the WLF equation, the ratio of $\text{ø}{}_{\mathrm{g}}\text{α}{}_{\mathrm{f}}$ (with α_f and ø_g being the difference in the volume expansion coefficients and the volume fraction ø at T_g, respectively), derived from the partition function, are in good agreement with the experimental values.     

Creep,creep recovery and dynamic mechanical measurements of a poly(propylene glycol) oligomer

Measurements have been made of the viscoelastic properties of a low molecular mass poly(propylene glycol), P4000, in shear creep and creep recovery. Taken together with previous dynamic mechanical measurements in alternating shear at frequencies of 30 MHz and 454 MHz and additional dynamic measurements at 40 kHz, it is shown that the observed behaviour can be ascribed to two processes. The major contribution can be associated with the normal modes of the polymer molecule as a whole but a significant contribution is attributed to motions of smaller backbone units, akin to the behaviour of supercooled non-polymeric liquids. The latter are described by a complex compliance which must first be inverted to the modulus form before addition to the summation of Rouse modes in order to calculate the effective overall modulus. Retardation times associated with motions of the backbone units overlap the relaxation times of the higher order Rouse modes which are apparently rendered inactive, the polymer mode contribution being accounted for by either the first or, at most, the first two Rouse modes. The equilibrium compliance, J⁰_e, decreases markedly with decreasing temperature within 15K above the glass transition temperature. At higher temperatures (>T_g + 15 K) J⁰_e decreases gradually with increasing temperature in agreement with calculations based upon the combined polymer mode and backbone processes. Particular care was necessary in order to obtain thoroughly dry samples of P4000: the presence of relatively small amounts of water increased the value of J⁰_e by up to four orders of magnitude.     

Effect of absorbed water on the thermal relaxation of biaxially stretched crosslinked poly(methyl methacrylate)

For three samples of the title materials the thermal relaxation characteristics were determined in rising temperature experiments and found to be dependent on water content. On heating, the polymers revert to the unstretched state and the onset temperature of this relaxation decreases with increasing water content. The most highly crosslinked polymers have the highest equilibrium water content at room temperature, the lowest relaxation onset temperature when saturated, and the highest relaxation onset temperature when dry. The effect of water on thermal relaxation is consistent with the observed depression of glass transition temperature. The relaxation of one of the materials was also studied isothermally. The effect of water is a temperature shift in the curve of log (maximum relaxation rate) against temperature. For a water content of 3.4 wt % this temperature shift is 25K, the same as the observed reduction in T_g. The effect of temperature on the maximum relaxation rate is of the form of the WLF equation. The apparent activation energy for thermal relaxation is lower in the saturated polymer.     

Changes in the dielectric relaxations of water in epoxy resin as a function of the extent of water ingress in carbon fibre composites

Dielectric relaxation measurements are reported over a frequency range from 10⁻¹ to 10⁹ Hz as a function of exposure time for an epoxy resin-carbon fibre composite, ageing at 60 °C in water. Investigation of the nature of the dipole relaxation of the water molecules, indicates the nature of their interaction with the polymer matrix. Analysis of the dielectric relaxation spectra allow identification of processes that can be attributed to ‘free’ and ‘bonded’ water, water in micro-cracking, located in carbon fibre disbonds and plasticizing the polymer matrix. Identification of the various types of location in which water exists was aided by use of the N_g factor from the Kirkwood-Frölich equation, which describes the constraints on free dipole ration nature imposed by the environment in which it is located. These data indicate the power of the dielectric technique for quantitative analysis of water ingress into epoxy composites.     

Rotating frame 1H n.m.r. spin-lattice relaxation studies of modified isotactic polypropylene

Rotating frame ¹H n.m.r. spin-lattice relaxation times T_1ϱ have been used to study relaxation processes in partially crystalline polypropylene and polypropylene modified by a copolymer of ethylene and alkylaminoacrylate. Measurements were carried out within the temperature range of 250–420 K. Three relaxation times T_1ϱ were detected over the whole temperature range. α_c relaxation in the crystalline regions of the polymer, relaxation processes β(U) and β(L), associated with an apparent double glass transition, and α_a relaxation process, which was ascribed to a free reorientation of the whole chains in the amorphous regions, were observed by temperature dependences of these relaxation times. In addition to the α_c relaxation, another relaxation process with relatively low molecular mobility was found in crystalline regions. The influence of the polymer modifier on the observed relaxation processes greatly depends on its amount.     

The effect of molecular weight and casting solvent on the miscibility of polystyrene-poly(α-methyl styrene) blends

The glass transition temperatures (T_g) have been measured for blends of polystyrene and poly(α-methyl styrene) in the molecular weight ranges: polystyrene, 2030 < M < 250 000, and poly(α-methyl styrene), 17 000 < M < 250 000. The presence of either one T_g or two has been used as a criterion to determine the miscibility of each blend over a range of compositions, and the T_gs were obtained from measurements of the temperature dependence of the heat capacities of the blends. A sinlge T_g was observed over the entire composition range for blends in which the component molecular weights were both less than 70 000 g mol^?1, when these were cast from toluene solutions. When propylene oxide solutions were used to prepare the blends, this limit dropped to M = 50 000 g mol^?1. By using the appearance of two T_gs as an indication that phase separation had taken place, it was possible to establish regions of miscibility and immiscibility as a function of casting solvent and molecular weight for both components. The change in heat capacity at the glass transition was measured and it was found that for miscible blends the heat capacity changes are similar to the calculated values, but for immiscible systems the measured change is smaller than expected.     

PVC modification with new functional groups. Influence of hydrogen bonds on reactivity, stiffness and specific volume

The chemical modification of PVC with new bifunctional thiol compounds is reported. Aliphatic as well as aromatic reactives were tested and the influence of protic and non-protic functionalities on reactivity was studied. The chemical structure of the polymers was analyzed using ¹H NMR spectroscopy.The structural changes in the modified samples were monitored by means of density and T_g determinations, which are a measure of interchain spacing and chain stiffness. While protic functionalities lead to polymers with strongly enhanced T_g values indicating a considerable stiffening of the system due to physical interaction by hydrogen bonds, the softening-point temperature of PVC modified with non-protic substituents does not change very much.The interchain spacing of the polymer is not significantly altered by the presence of mobile hydrogen in the polymer.     

Interactions of binary liquid mixtures with polysaccharides studied using multi-dimensional NMR relaxation time measurements

Nuclear magnetic resonance transverse T₂ relaxation time has proven to be a valuable parameter for characterizing liquid/polymer interactions. This measurement is applicable to many food, personal care, and cosmetic products that contain multi-component liquid mixtures. Here, we investigate the interactions of corn starch with water/glycerol mixtures of different weight compositions and explore liquid exchange dynamics; such a system is relevant to the personal care industry. We use a combination of chemical shift resolved ¹H T₂ relaxation measurements and corresponding two-dimensional T₂ relaxation exchange experiments using both a conventional experimental protocol and a modified method with the addition of NMR chemical shift selectivity. Two relaxation regimes were evident for the hydroxyl ¹H (found in both water and glycerol) whilst three relaxation regimes are evident for the aliphatic glycerol ¹H associated here with strongly bound, weakly bound, and free (bulk) liquid, respectively. At higher water contents preferential absorption of glycerol was evident. T₂-T₂ exchange maps with a range of storage times reveal molecular exchange rates between all three regimes due to self-diffusion. Rapid exchange of water between the bulk and bound locations was evident in the case of pure water. Exchange rates for hydroxyl ¹H was considerably reduced by the inclusion of glycerol.