Dispersions of polymer ionomers: I

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.     

Relaxation processes in room temperature ionic liquids: the case of 1-butyl-3-methyl imidazolium hexafluorophosphate

A detailed investigation on the nature of the relaxation processes occurring in a typical room temperature ionic liquid (RTIL), namely, 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF(6)]), is reported. The study was conducted using both elastic and inelastic neutron scattering over a wide temperature range from 10 to 400 K, accessing the dynamic features of both the liquid and glassy amorphous states. In this study, the inelastic fixed energy scan technique has been applied for the first time to this class of materials. Using this technique, the existence of two relaxation processes below the glass transition and a further diffusive process occurring above the glass-liquid transition are observed. The low temperature processes are associated with methyl group rotation and butyl chain relaxation in the glassy state and have been modeled in terms of two Debye-like, Arrhenius activated processes. The high temperature process has been modeled in terms of a Kohlraush-Williams-Watts relaxation, with a distinct Vogel-Fulcher-Tamman temperature dependence. These results provide novel information that will be useful in rationalizing the observed structural and dynamical behavior of RTILs in the amorphous state.     

Dipolar motions and phase transitions in a side‐chain polysiloxane liquid crystal. A study by thermally stimulated depolarization currents

The relaxation mechanisms present in a side‐chain liquid crystalline polymer have been studied by Thermally Stimulated Depolarization Currents (t.s.d.c.), in a wide temperature range covering the glassy state, the glass transition region, and the liquid crystalline phase. The thermal sampling procedure was used to decompose the complex relaxations into its narrowly distributed components. Three relaxation mechanisms were observed in this polymer: a relaxation below the glass transition temperature that is broad and extends from −150°C up to −110°C, the glass transition relaxation whose maximum intensity appears at ∼20°C, and a relaxation above the glass transition temperature, in the liquid crystalline phase. The attribution of these relaxations at the molecular level is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 227–235, 1999     

Broadband dielectric study of the glass transition in poly(ethyleneglycol)-water mixture

We performed broadband dielectric measurements of a polyethyleneglycol-water mixture in the frequency range between 10 GHz and 1 microHz and the temperature range between 300 and 133 K. One relaxation process is observed throughout the whole temperature range. The temperature dependence of the relaxation time clearly obeys the Vogel-Fulcher law above 183 K, and the Arrhenius law below 183 K. This observed relaxation process is the secondary process, and the primary process related to the glass transition is masked by the low-frequency ionic contribution below 183 K. The glass transition concerned with the masked primary process leads to the Vogel-Fulcher to Arrhenius transition of the secondary process.     

Orientational and translational dynamics in room temperature ionic liquids

The authors investigate the dynamics of a series of room temperature ionic liquids, based on the same 1-butyl-3-methylimidazolium cation with different anions, by means of broadband (10(-6)-10(9) Hz) dielectric spectroscopy and depolarized light scattering in the temperature range from 400 K down to 35 K. Typical ionic conductivity is observed above the glass transition temperature Tg. Below Tg the authors detect relaxation processes that exhibit characteristics of secondary relaxations, as typically observed in molecular glasses. At high temperatures, the characteristic times of cation reorientation, deduced from the light scattering data, are approximately equal to the electric modulus relaxation times related to ionic conductivity. In the supercooled regime and close to Tg, the authors observe decoupling of conductivity from structural relaxation. Overall, room temperature ionic liquids exhibit typical glass transition dynamics, apparently unaltered by Coulomb interactions.     

Investigation of dielectric relaxations associated with the glass transition of vinylidene fluoride and trifluoroethylene copolymers by thermally stimulated current

Thermostimulated current (TSC) spectroscopy was applied to the characterization of dielectric relaxations associated with the glass transition of a series of P(VDF/TrFE) copolymers. The maximum temperature of the β-mode increases slightly as the TrFE unit content is increased, in the same manner as the glass transition temperature. By using the technique of fractional polarizations to the resolution of this relaxation mode, we have isolated, for all the polymers investigated, a series of elementary relaxation times that obey a compensation law. This behavior is characteristic of the free amorphous phase of polymers. The mean activation energy of this mode increases as the TrFE unit content is increased, due to a stiffening of molecular chains. Annealing of the copolymers above their ferroelectric-to-paraelectric transition induces a strong crystallinity increase of the materials. As a matter of fact, the amorphous phase is squeezed in to dimensions lower than the characteristic length scale associated with the glass transition. © 1995 John Wiley & Sons, Inc.     

Dynamic melt rheology of poly(styrene-co-vinylpyridine) and their methyl iodide salts

The dynamic melt rheology of random copolymers of polystyrene with 2–9 mol% 4-vinylpyridine was examined in their quaternized and nonquaternized forms. Time–temperature reducibility applies in all cases. Relative to the glass transition, the master curves of the nonquaternized materials are identical. Melt flow in the quaternized materials is mildly retarded, the extent increasing with ion content. At the highest ion contents, the relaxation processes appear to be of Arrhenius type. As in the glass transition region, the ionic interactions in the plateau and terminal zones are thermally labile.     

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.     

Ion dynamics under pressure in an ionic liquid

We investigate ion dynamics under pressure in the ionic liquid 1-butyl-1-methylpyrrolidinium bis[oxalate]borate (BMP-BOB) by conductivity relaxation measurements in the temperature range 123-300 K and varying pressures from 0.1 MPa up to 0.5 GPa. We report on the influence of pressure on the relaxation times and on the spectral shape of the conductivity relaxation process. We also analyze the pressure dependence of the glass transition temperature and find that the dynamic response under pressure in this ionic liquid shows remarkable similarities to nonionic glass formers. The main relaxation process shows temperature-pressure superposition while a secondary relaxation process, very weakly depending on pressure, is observed. The spectral shape of the main relaxation broadens with increasing pressure or decreasing temperature, but is found to be the same when the relaxation time is the same, independently of the particular pressure and temperature values.     

Effect of chain length on fragility and thermodynamic scaling of the local segmental dynamics in poly(methylmethacrylate)

Local segmental relaxation properties of poly(methylmethacrylate) (PMMA) of varying molecular weight are measured by dielectric spectroscopy and analyzed in combination with the equation of state obtained from PVT measurements. Significant variations of glass transition temperature and fragility with molecular weight are observed. In accord with the general properties of glass-forming materials, single molecular weight dependent scaling exponent gamma is sufficient to define the mean segmental relaxation time taualpha and its distribution. This exponent can be connected to the Gruneisen parameter and related thermodynamic quantities, thus demonstrating the interrelationship between dynamics and thermodynamics in PMMA. Changes in the relaxation properties ("dynamic crossover") are observed as a function of both temperature and pressure, with taualpha serving as the control parameter for the crossover. At longer taualpha another change in the dynamics is apparent, associated with a decoupling of the local segmental process from ionic conductivity.     

A structural interpretation of the two components governing the kinetic fragility from the example of interpenetrated polymer networks

Kinetic fragility and cooperativity length, two major characteristics of the relaxation dynamics at the glass transition, are, respectively, investigated by dynamic mechanical analysis and modulated temperature differential scanning calorimetry in a series of interpenetrated polymer networks based on acrylate and epoxy systems. The relaxation dynamics are impacted by two variables: the rigidity of the network, and the structural heterogeneity resulting from blending. However, the fragility and the cooperativity do not vary similarly. The glass transition progressively broadens as the mass fractions of acrylate and epoxy become equivalent, leading to a strong decrease in cooperativity. On the other hand, under the same conditions, the fragility transitions between the lower value of pure acrylate and the higher value of pure epoxy. This divergence helps concluding that the variations in the temperature dependence of the relaxation time are not purely related to the more or less cooperative nature of the glass transition. By splitting the fragility index in a volume contribution and an energetic contribution, it is shown that the contribution of cooperativity to the variations of the relaxation time with temperature is increased under two structural conditions: low backbone rigidity and high intermolecular interactions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1393–1403     

Glass Transition Behavior in Se-Rich Ge-Se Alloys

Differential scanning calorimetry (DSC) was utilized to study the behavior of six Ge-Se glasses containing 0, 5, 10, 15, 17.5 and 20 at.% Ge during the glass transition. These alloys readily form glasses and can be prepared by quenching in air. Moreover, their behavior depends greatly on the composition. This work reveals that two additional properties must be considered: the variation in the glass transition temperature and different structural relaxation. The quantity used to quantify the relaxation was the enthalpy relaxation as this measures the heat lost by the glass during annealing. Given the complexity of the relaxation process, the experimental results were analysed by means of the empirical Kohlrausch-Williams-Watts relaxation model. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hierarchical structure and dynamics of an ionic liquid 1-octyl-3-methylimidazolium chloride

We have performed the heat capacity, neutron diffraction, and neutron quasielastic scattering measurements of an ionic liquid 1-octyl-3-methylimidazolium chloride (C8mimCl). The heat capacity data revealed that C8mimCl exhibits a glass transition with a large heat capacity jump at T(g) = 214 K, which is lower than T(g) of C4mimCl with a shorter alkyl-chain. In the neutron diffraction measurement for a deuterated analogue, d-C8mimCl, the peaks associated with the inter-domain, inter-ionic, and inter-alkyl-chain correlations appeared at (3, 11, and 14) nm(-1), respectively. The temperature dependence of these peaks indicates that the packing of the alkyl-chains becomes more compact and the domains become more vivid and larger as decreasing temperature. The quasielastic neutron scattering measurements using neutron spin echo and time-of-flight type instruments demonstrated that C8mimCl has faster relaxations probably owing to the alkyl-group and a slower relaxation owing to the ions. The latter relaxation, which is related to the glass transition, is of non-exponential as in the α relaxation of glass-forming molecular liquids. The relaxation of domains could not be observed in the present experiment but should have relaxation times longer than 100 ns. This is the first report to clarify temperature dependence of the hierarchical structure and relaxations simultaneously for a typical ionic liquid.     

Relaxation dynamics and ionic conductivity in a fragile plastic crystal

We report a thorough characterization of the dielectric relaxation behavior and the ionic conductivity in the plastic-crystalline mixture of 60% succinonitrile and 40% glutaronitrile. The plastic phase can be easily supercooled and the relaxational behavior is investigated by broadband dielectric spectroscopy in the liquid, plastic crystalline, and glassy crystal phases. The α-relaxation found in the spectra is characterized in detail. A well-pronounced secondary and faint indications for a third relaxation process were found. The latter most likely is of Johari-Goldstein type. From the temperature dependence of the α-relaxation time, a fragility parameter of 62 was determined. Thus, together with Freon112, this material stands out among all other plastic crystals by being a relatively fragile glass former. This finding provides strong support for an energy-landscape related explanation of the fragility of glass formers. In addition, unusually strong conductivity contributions were detected in the spectra exhibiting the typical features of ionic charge transport making this material a good basis for solid-state electrolytes.     

Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization

The hydrophobic ionic liquid 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was successfully used as solvent in group transfer polymerization of traditional methacrylates (methyl methacrylate, n‐butyl methacrylate, and benzyl methacrylate) and of ionic liquid methacrylates (ILMAs). This demonstrates that this ionic liquid makes reaction conditions, which do not require the use of ultra‐dried solvents. The ILMAs were N‐[2‐(methacryloyloxy)ethyl]‐N,N‐dimethyl‐N‐alkylammonium bis(trifluoromethylsulfonyl)imides bearing methyl, ethyl, propyl, butyl, or hexyl substituents. Increasing size of the alkyl substituent at the cation results in decreasing glass transition temperature in case of both ionic liquid methacrylates and polymers derived of them. Furthermore, the glass transition temperature is significantly higher for these polymers compared with the ionic liquid methacrylates, and the effect of glass transition temperature reduction with increasing size of the alkyl substituent is stronger for the polymers. A mechanism was proposed explaining the catalytic function of the ionic liquid used as solvent for polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2849–2859     

Relationship between the α‐ and β‐relaxation processes in amorphous polymers: Insight from atomistic molecular dynamics simulations of 1,4‐polybutadiene melts and blends

Amorphous polymers exhibit a primary (glass, or α‐) relaxation process and a low‐temperature relaxation process associated with polymer backbone motion usually referred to as the β‐relaxation process. The latter process can be observed below the glass transition temperature of the polymer and usually merges with the α‐relaxation process at temperatures somewhat above the glass transition temperature. While it is widely held that both the α‐relaxation and β‐relaxation processes are engendered by localized (segmental) motions of the polymer backbone, and that there is a strong mechanistic connection between them, the molecular mechanisms of the α‐relaxation and β‐relaxation processes in amorphous polymers are not well understood. Recently, atomistic molecular dynamics simulations of melts and blends of 1,4‐polybutadiene have provided insight into the relationship between the α‐ and β‐relaxation processes in glass‐forming polymers and an improved understanding of their molecular origins. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 627–643, 2007     

Molecular mobility of substituted poly(p-phenylenes) characterized by a range of polymer relaxation techniques

The free volume and related mobility properties of substituted poly(p-phenylene) polymers are examined. The techniques used range from positron annihilation, dielectric relaxation, and dynamic mechanical spectroscopy to thermally stimulated currents. Fractional free volume is determined for the samples with different substituted side groups and related to the glass transition temperature. Bulkier groups lead to a greater fractional free volume and lower glass transition temperatures. Comparison of molecular relaxation times using the different characterization techniques demonstrates that there is strong coupling between motion of the main chain and the side groups, on which the dipoles reside. Intermolecular coupling between the main chains at the primary relaxation is shown in this work to be related to the nature of the side chains and resultant free volume, as are the temperature locations of local, secondary relaxations. A qualitative model describing the effect of regiochemistry on the motions and packing of these materials is also proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1465–1481, 1998     

Calorimetric study and modeling of molecular mobility in amorphous organic pharmaceutical compounds using a modified Adam-Gibbs approach

The purpose of this study is to provide a quantitative characterization of the thermal behavior of amorphous organic pharmaceutical compounds across their glass transition temperature, and to assess their molecular mobility as a function of temperature and time by combining theoretical simulations with experimental measurements using differential scanning calorimetry. A computational approach built on the Boltzmann superposition principle of nonexponential decay and the Adam-Gibbs theory of entropic-dependent structural relaxation is presented. The heat capacities of the crystalline and amorphous forms are incorporated into the simulation in order to accurately assess the entropic fictive temperature as functions of temperature and time under any arbitrary set of experimental conditions. Using this method, we evaluated properties of the glass former, D and T0, and the nonexponentiality index beta, for amorphous salicin, felodipine, and nifedipine, by fitting the simulated glass transition profile with the experimentally determined heat capacity across the glass transition region. From this fit, the evolution of the relaxation time of the model compounds following any thermal cycle, including heating, cooling, and isothermal holds can then be estimated a priori. This study reveals the profound and inextricable effect of thermal history on the molecular mobility of the amorphous materials, and the ability of the glass to undergo fast changes in its molecular motions over an aging process even at low temperatures.     

Universal scaling, dynamic fragility, segmental relaxation, and vitrification in polymer melts

Our theory of dynamic barriers, slow relaxation, and the glass transition of polymers melts is numerically applied using parameters relevant to real materials. The numerical results are found to be in qualitative agreement with all the approximate analytic expressions previously derived with quantitative differences on the order of approximately 20-30% or much less. The analytic prediction of a universal temperature dependence of the alpha relaxation time, and its intimate connection with the idea of a nearly universal crossover time, is established. Inter-relations between the breadth of the deeply supercooled regime, two definitions of the dynamic fragility, and the magnitude of the fast local Arrhenius process at the glass transition temperature are demonstrated and system-specific limitations identified. A quantitative application to segmental relaxation over 16 orders of magnitude in a polyvinylacetate melt yields encouraging results regarding the accuracy of the theory. The theoretical relaxation time results are well fit by multiple empirical forms (generally containing an assumed singular aspect) using parameters consistent with experimental studies. No physical significance is ascribed to this finding, but it does provide additional support for the temperature dependence of the alpha relaxation process predicted by the theory.     

An upper limit to kinetic fragility in glass-forming liquids

The kinetic fragility of a liquid is correlated to the magnitude of enthalpy hysteresis in various glass-forming materials during thermal cycling across the glass transition. While the lower bound of liquid fragility is well known, there has been little research into the possibility of an inherent upper limit to fragility. In this paper, we present a theoretical argument for the existence of a maximum fragility and show that the correlation between fragility and enthalpy hysteresis allows for an empirical evaluation of the upper limit of fragility. This upper limit occurs as the enthalpy hysteresis involved in thermal cycling about the glass transition approaches zero, leading to m(max)≈175. This result agrees remarkably well with our previous estimate. The dynamics of maximum fragility liquids are discussed, and a critical temperature of ～1.5 T(g) (where T(g) is the glass transition temperature) is revealed where a transition from nonexponential to exponential structural relaxation occurs.