Criteria of efficiency of cellulose acetate plasticization

Using cellulose acetate plastics as an example, it was shown that the search for the optimal concentrations of plasticizers should take into account the compatibility of components, as well as the thermophysical and mechanical properties of plasticized polymers. It was suggested that the temperature range of durability of a plastic, i.e., the difference between its glass-transition and brittle temperatures, be used as a plasticization efficiency criterion. Plasticizers that are well compatible with a polymer at processing temperatures but show a limited compatibility at its service temperatures make it possible to manufacture goods with an extended durable temperature range.     

Plasticization of ultra-thin polysulfone membranes by carbon dioxide

Plasticization of gas separation membranes by carbon dioxide permanently alters their performance and increases the possibility of membrane failure. This is amplified in ultra-thin composite membranes, where the active polymeric layer is less than 2 μm. Here, the plasticization influence of CO₂ is measured on ultra-thin polysulfone composite membranes for a range of active layer thicknesses, at four temperatures. The resulting permeability–pressure isotherms demonstrate plasticization occurs for all thicknesses at pressures lower than has been reported for dense membranes. These isotherms were quantitatively fitted with an expanded dual-sorption model that takes into account plasticization of the membrane. The plasticization potential of CO₂ for polysulfone was found to increase with reduced active layer thickness. Similarly, the plasticization potential of CO₂ was found to decrease with temperature. These results are consistent with similar research that shows that thin films behave differently to dense membranes.     

Separation of cationic and anionic conductivity constituents in solid polymer electrolytes comprising a copolymer of acrylonitrile and butadiene (40:60) and lithium hexafluoroarsenate

A technique for separating cationic and anionic constituents of the ionic conductivity of amorphous solid polymer electrolytes in the region of low salt concentrations is proposed. The technique employs model equations for separately describing transport of cations and anions that differently interact with the polymer matrix. It is shown that the temperature dependences of the anionic conductivity obey the Vogel-Tamman-Fulcher equation and those of the cationic conductivity, the Miyamoto-Shibayama equation. By separating the overall ionic conductivity into constituents, cationic transport numbers are evaluated in broad ranges of salt concentrations and temperatures in the system comprising a copolymer of acrylonitrile and butadiene (40:60) and lithium hexafluoroarsenate. At nearly ambient temperatures the anionic constituent is predominant. Two different cation transport mechanisms are established at elevated temperatures.     

Effect of Lithium Tetrafluoroborate on the Solubility of Carbon Dioxide in the Ionic Liquid 1-Butyl-3-Methylimidazolium Tetrafluoroborate

In this work, the phase behavior of the ternary system of carbon dioxide +1-butyl-3-methylimidazolium tetrafluoroborate?+?lithium tetrafluoroborate has been investigated. Mixtures of known concentrations of the salt, ionic liquid and carbon dioxide were prepared and their bubble point pressures were measured at different temperatures. Results are reported for this ternary system, at carbon dioxide concentrations of 20.2, 27.6 and 35.2?mol-% and salt concentrations of 0.0, 6.0, 11.5, 16.3 and 21.1?mol-% (on a carbon-dioxide free basis) and within temperature and pressure ranges of 293.15?C358.15?K and 1.2?C11.3?MPa, respectively. It was observed that the addition of the salt increased the bubble point pressure and its effect was concentration-dependent, i.e. at higher concentrations of the salt, higher pressures are required. This behavior is greater at higher temperatures.     

Water absorption of a diglycidyl ether of bisphenol A/1,3-bisaminomethylcyclohexane (DGEBA/1,3-BAC) epoxy resin system

The diffusive and dynamic mechanical behavior of the DGEBA/1,3-BAC epoxy resin system was studied during water absorption. The diffusion of water was investigated at 100% relative humidity, by immersion of specimens in water at 60, 80 and 100°C. In all absorption experiments, water diffusion followed Fick's law. Diffusion coefficients and saturated water concentrations are given for these temperatures. The activation energy for diffusion was determined from the relationship between the diffusion coefficient and the reciprocal of the absolute temperature. The value obtained was 31.2 kJ mol^–1. Dynamic mechanical analysis of samples immersed in 100°C water and with various water contents showed both a shift of T_g, defined by thetan peak, to lower temperatures and a slight decrease in the dynamic modulus in the presence of water. These effects are probably a result of plasticization.This work was supported by the Xunta de Galicia through grant XUGA-17201A92.     

Plasticization mechanism in polybenzimidazole membranes for organic solvent nanofiltration: Molecular insights from in situ FTIR spectroscopy

Despite substantial research efforts being devoted to design polymer membranes for organic solvent nanofiltration (OSN) exhibiting enhanced plasticization resistance, detailed studies of membrane structural stability in chemically challenging environments are rare. This study sets forth a multiscale method, which combines in situ FTIR measurements in the transmission mode with sorption and transport measurements, to investigate the molecular mechanism of polymer plasticization upon exposure to organic species. We recently reported that polybenzimidazole (PBI), a polymer that has been considered for OSN application, experiences severe plasticization upon exposure to methanol. FTIR measurements suggest that the mechanism of PBI plasticization relies on competitive hydrogen bonding. According to this mechanism, methanol molecules disrupt the hydrogen bonded network characteristic of dry PBI, by forming mutual polymer/penetrant hydrogen bonds, which enhances polymer chain mobility and favors polymer plasticization. The analysis of the isosteric heat of sorption supports the picture sketched above. The method developed in this study can be readily extended to many other systems of practical interest in membrane science, to shed fundamental light on the phenomenon of plasticization, whose molecular aspects are still largely unknown. Equally important, this study provides some useful guidelines to design OSN membrane materials.     

Phase Transitions of MBBA Confined in Porous Solids

The diffusive and dynamic mechanical behaviour of an epoxy system containing tetraglycidyl-4,4′-diaminodiphenylmethane and a multifunctional Novolac glycidyl ether cured with 4,4′-diaminodiphenylsulfone was studied after water sorption. The diffusion of water was performed at 100% relative humidity, by immersion of specimens in water at 20, 40, 70 and 100°C. In all sorption experiments, the water diffusion followed Fick's law. Diffusion coefficients and saturated water concentrations were estimated for these temperatures. The activation energy for diffusion was determined from the relationship linking the diffusion coefficient and the reciprocal of the absolute temperature. The value obtained was 45.7 kJ mol^-1. Dynamic mechanical analysis of samples immersed in water at 25 and 100°C, and with various water contents, showed a shift in T_g> (defined by the tanδ peak) to lower temperatures over the glass transition region, and a slight decrease in the dynamic storage modulus in the presence of water as a result of a plasticization effect. This revised version was published online in July 2006 with corrections to the Cover Date.     

Moisture effect on the low- and high-temperature dielectric relaxations in nylon-6

The effect of water sorption on the dielectric relaxation processes of nylon-6 samples with water concentrations ranging from the dry to the water-saturated polymer has been studied by thermally stimulated depolarization currents experiments in a broad temperature range, from 77 to 365 K. The strengths of the low-temperature modes, γ- and β-peaks, are affected in opposite ways by the water concentration, h, as the first one shows a decrease in intensity and the second one grows as h increases. The precise determination of the relaxation parameters is made by the decomposition in elementary Debye processes and best fitting to the experimental profile of the complex peak. For h < 3%, the reorienting energies are almost independent of the water content, and the most significant intensity variations occur. The firmly bound water is held responsible for these effects. As for the higher temperature zone besides the α-peak, which is the dielectric manifestation of the glass transition, intermediate temperatures modes are observed at high h values and are originated by the loosely bound water, while the highest temperature peak is attributed to a Maxwell–Wagner interfacial polarization. The characteristic parameters of the α-mode are determined and related to the plasticization effect of water. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2879–2888, 1997     

Defect interactions in alkali halides

Pairwise defect interactions between divalent cation impurities, cation vacancies and anion vacancies have been studied in the extrinsic and intrinsic temperature ranges for the KClSr²⁺ system. Pair correlation functions have been derived for the various defect interactions distinguished by their site symmetries and these show the existence of associated divalent cation—cation vacancy and cation—anion vacancy pairs even at high temperatures. Pair formation gives way to dissociation at low impurity concentrations and high temperatures.     

Preparation and Characterization of Poly(Lactic Acid)-g-Maleic Anhydride + Starch Blends

Poly(lactic acid) (PLA) and starch copolymers are obtained by reactive blending - varying the starch compositions from 0 to 60%. PLA is functionalized with maleic anhydride (MA), obtaining PLA-g-MA copolymers using dicumyl peroxide as an initiator of grafting in order to improve the compatibility and interfacial adhesion between the constituents. PLA + starch blends without a compatibilizer do not have sufficient interfacial adhesion. Decomposition temperature of PLA is not affected by grafting. Glass transition temperatures and dynamic mechanical properties are affected since MA has a plasticizing effect. Along with an increasing starch content friction decreases while wear loss volume in pin-on-disk tribometry has a minimum at nominal 15% wt. starch but increases at higher starch concentrations. The residual depth in scratching and sliding wear testing has a maximum at 15% starch; there is a minimum of storage modulus E′ determined in dynamic mechanical testing at the same concentration. Microhardness results also reflect the plasticization by MA.     

Activity behaviour of electrolyte solutions: Evaluation of temperature effects by means of the quasi-random lattice model

The paper presents some applications of the Moggia–Bianco (quasi-random lattice) model for the calculation of mean activity and osmotic coefficients of electrolyte solutions, with emphasis on temperature effects. Aqueous uni-univalent and uni-divalent electrolytes from 0 °C to 100 °C are considered. Results show that the model is in general applicable over wide ranges of concentrations and temperatures, despite its dependence on a unique fitting parameter (which is, sometimes, experimentally known).Some theoretical aspects of the model are investigated. Hydration diameters are evaluated for uni-univalent systems. Concerning uni-divalent systems, charge-asymmetry effects are accounted for more rigorously than in previous works, starting from a better assessment of the relationship between the behaviour of the electrolyte at very low concentrations and the behaviour occurring at high concentrations.     

A novel method to characterize thermal properties of the polymer and gas/supercritical fluid mixture using dielectric measurements

Gases or supercritical fluids (SCF) are widely used in polymer science and engineering, as their dissolution into polymeric materials will alter their inherent thermal properties; including melting and crystallization temperatures (T_m and T_c). One possible method to determine these temperatures, at elevated pressures, is to use a high-pressure differential scanning calorimeter (HP-DSC). However, the elevated pressures used in HP-DSC may result in signal instabilities, limiting the testing window for these pressures. This study presents a novel testing system using dielectric measurements to determine the effects of dissolved gas/SCF on the T_m and T_c of polymers. We have developed an instrument to determine the dielectric properties of both polymer/gas and polymer/SCF mixtures, at elevated pressures and temperatures. Using the change in the measured dielectric constant or loss, T_m and T_c were determined. The effects of hydrostatic pressure and plasticization due to dissolved carbon dioxide (CO₂) and Helium (He) on the T_m and T_c of high density polyethylene (HDPE) are presented and discussed. Both T_m and T_c increase with pressure and decrease due to plasticization, i.e., pressure and plasticization are competing variables. The dissolution of He, having a low solubility into HDPE, reveals that pressure is the dominant effect. In contrast, the dissolution of CO₂, having a high solubility into HDPE, shows that plasticization is predominant.     

Thermal treatment of dense polyimide membranes

A study has been conducted to clarify the relationship between polymer structure, annealing temperature, and the extent of plasticization by high‐pressure CO₂ for two typical polyimide membranes; BTDA‐DAPI (poly(3,3′‐4,4′‐benzophenone tetracarboxylic–dianhydride diaminophenylindane) and 6FDA‐TMPDA (poly(2,2′‐bis(3,4′‐dicasrboxyphenyl) hexafluoropropane dianhydride–2,3,5,6‐tetramethyl‐1,4‐phenylenediamine). Both membrane materials are exposed to varying levels of thermal annealing at 200 and 250 °C. The effect of this heat treatment on free volume is examined using positron annihilation lifetime spectroscopy (PALS), whereas fluorescence spectroscopy is used to monitor changes in electronic structure. Results show that thermal annealing causes a reduction in both the size and number of free volume elements. A strong relationship is found between the fluorescence peak intensity for 6FDA‐TMPDA and both the membrane gas permeability and plasticization pressure. This correlation is most likely the result of the formation of charge transfer complexes, particularly at 250 °C. However, the formation of covalent crosslinks at these temperatures cannot be discounted. No fluorescence is observed for BTDI‐DAPI. Although thermal annealing has a significant effect on the extent of plasticization in both polymers, it is found that the rate of plasticization is unaffected by the annealing temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1879–1890, 2008     

Electric relaxation currents in a cured polyester resin with nitroaniline additives

The influence of a small amount of nitroaniline additive on the thermally stimulated discharge current in a cured polyester resin was investigated. The height of dipole relaxation and space charge relaxation peaks increased and the maxima of the dipole peaks shifted to lower temperatures. The observed effects are explained by the nitroaniline—polyester resin interaction, which causes a structural plasticization of the polymer.     

Carbon-13 spin-lattice relaxation studies of the effect of water on ion-selective electrode membranes

(13)C spin-lattice relaxation studies on bis(2-ethylhexyl) adipate (DOA) plasticized poly(vinylchloride) (PVC) membranes are reported for plasticization levels ranging from 25 to 100 wt% plasticizer. The interaction between DOA and PVC molecules in these membranes appears to involve an entrapment of the plasticizer molecule within the polymer matrix. This is based on the constancy of the characteristic segmental motions of the plasticizer chains throughout the concentration range studied. The segmental mobility of the plasticizer component is modified by water absorption in the membrane. The pattern of characteristic segmental motions of the plasticizer is altered, the effect depending on the amount of added salt in the membrane. The results show water has a weak influence on the microviscosity of the membrane matrix.     

Polyimide hollow fiber gas separation membranes: preparation and the suppression of plasticization in propane/propylene environments

Asymmetric hollow fiber membranes were prepared using the polyimide Matrimid^® 5218. The fibers had an effective top layer thickness of 0.3–0.4 μm. The fibers were used in propane and propylene permeation experiments. Whereas the propane permeance remained more or less constant, the propylene permeance increased with feed pressure greater than 1 bar. This indicated that propylene plasticized the membrane material.The fibers were given different heat-treatments in order to investigate the possibilities to suppress the propylene plasticization. This treatment also reduced the permeance considerably, the effect being more pronounced the more intense the heat-treatment was. This was in agreement with scanning electron microscopy studies, which revealed that densification of the fibers occurred due to the heat-treatments. Most important, relatively mild heat-treatments already appeared to be effective in suppressing the propylene plasticization. Since these heat-treated fibers still readily dissolved it is concluded that the plasticization suppression was not due to crosslinking, but to an annealing effect. Due to thermal curing (annealing) at temperatures below the T_g aromatic polyimides tend to form charge transfer complexes, which restrict the polymer chain mobility. Presence of these complexes seems to be responsible for suppression of propylene plasticization.     

Development of asymmetric 6FDA-2,6DAT hollow fiber membranes for CO2/CH4 separation: Part 2. Suppression of plasticization

We have studied the CO₂-induced plasticization phenomenon of asymmetric poly(2,6-toluene-2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane diimide) (6FDA-2,6 DAT) hollow fiber membranes for CO₂/CH₄ applications. Several processing and thermal approaches have been investigated to study their effectiveness to enhance anti-plasticization characteristics. Experimental results indicate that hollow fiber membranes spun at different shear rates and take-up rates cannot effectively suppress the CO₂ induced plasticization. Thermally treated 6FDA-2,6 DAT hollow fiber membranes show significant reduction in CO₂-induced plasticization. Wide-angle XRD spectra reveal no visible change in d-space after thermal treatment, while solubility data imply no cross-links occurred. Scanning electron microscopy (SEM) pictures illustrate heat treatment results in more compact selective-skin layer and substructure, thus strengthening the anti-plasticization characteristics of hollow fibers. By considering the degree of plasticization, dense-layer thickness, and heat treatment temperature, an optimal temperature of 250 °C (for 5 min) is identified for the heat treatment of 6FDA-2,6 DAT hollow fiber membranes. NMR spectra suggest the cause of forming a highly densified skin after heat treatment is mainly due to chain relaxation and enhanced nodule interaction at elevated temperatures.     

Mobility of CD4 molecules in nanoscale cages of zeolites as studied by deuteron NMR relaxation

Deuteron spin–lattice relaxation was applied to study mobility of CD₄ molecules trapped in the cages of zeolite NaY. There are two, interconnected sets of cages: α-cages and β-cages with 1.16 and 0.74 nm diameter, respectively. The relaxation temperature dependence, measured between 4 and 300 K, can be divided into four ranges with characteristic motional parameters. At higher temperatures exchange between cages dominates. Increasing rate of translational motion leads to a significant reduction of the relaxation rate. Features typical for quantum rotors were observed at low temperatures. Molecules in the α-cages exhibit reorientational freedom, while motion of these in β-cages is significantly restricted. Increasing abundance of molecules in β-cages indicates slow diffusion down to low temperatures.     

Natural radioactivity in granites and gneisses of the Opava Mountains (Poland): a comparison between laboratory and in situ measurements

The natural radioactivities of five characteristic igneous rocks of the eastern foreland of the Opava Mountains (Eastern Sudetes, Poland), obtained in the laboratory and under in situ conditions, are presented. The activity concentrations of ²³²Th, ²³⁸U, and ⁴⁰K were measured using an HPGe gamma-ray spectrometry system. The ranges of the activity concentrations of ²³²Th were 7–71 Bq kg^?1 in the laboratory and 6–68 Bq kg^?1 for the in situ measurements. For ²³⁸U, the ranges of the activity concentrations were 5–52 Bq kg^?1 in the laboratory and 9–48 Bq kg^?1 for the in situ measurements, and for ⁴⁰K, the ranges were 520–1560 Bq kg^?1 in the laboratory and 537–1700 Bq kg^?1 for the in situ measurements. These determined activity concentrations were compared with the average activity concentrations of the radionuclides in similar types of rocks and with data from the Sudetes available in the literature. No significant differences were found between the in situ and laboratory measurements.