Effect of antiplasticization on selectivity and productivity of gas separation membranes

Addition of certain low molecular diluents cause glassy polymers to become stiffer owing to reduced rates of segmental motions. This antiplasticization response is accompanied by a decrease in permeability to gases and may be accompanied by either an increase or a decrease in the selectivity of transport for any two gases. When compared to the trade-off between selectivity and productivity of gas separation membranes made from a variety of polymer structures, antiplasticization does not offer any advantageous combination of these traits for either polysulfone or poly(phenylene oxide). However, this approach may have value when increased selectivity at the expense of productivity is justified but developing membranes from another polymer is not desirable.     

Solid state NMR investigation of antiplasticization of polystyrene by mineral oil

The effects of mineral oil plasticization of polystyrene were investigated as a function of polystyrene molecular weight and mineral oil concentration. Solid state NMR, thermo/mechanical methods and positron annihilation spectroscopy (PAS) were used to study the molecular dynamics and free volume effects of this blend. Antiplasticization was observed in the low (40,000) molecular weight polystyrene samples as an embrittlement of the system. In contrast, the flexural modulus was not affected by the presence of mineral oil in the higher (270,000) molecular weight polymers but a decrease in the flexural strength was observed with increasing mineral oil concentration. The NMR and PAS data indicated that the mineral oil was not dissolved in the polymer at ambient temperature, rather it phase separated even at very low concentrations. This caused antiplasticization in low molecular weight polymers because the small free volume holes were filled causing a densification of the system. With high molecular weight polystyrene, this phase separation was manifested as a decrease in the flexural strength.     

Effect of antiplasticization on gas sorption and transport. I. Polysulfone

The addition of tricresyl phosphate, N-phenyl-2-naphthylamine, and 4,4′-dichlorodiphenyl sulfone to polysulfone causes changes in thermal and mechanical properties of the glassy mixtures associated with antiplasticization, i.e., reduction in glass transition temperature and increase in stiffness. These changes are also found to be accompanied by reductions in sorption of carbon dioxide and the permeability coefficients for helium, carbon dioxide, and methane at low diluent concentrations with reversal of these trends at higher levels as also occurs for the mechanical properties. Detailed analyses of data for carbon dioxide are given in terms of the dual sorption and mobility models often used for glassy polymers. The mobility for gas transport was found to decrease with diluent addition. The major cause for the decreased sorption is the reduction in glass transition temperature accompanying addition of the diluents. The changes in transport behavior approximately parallel the changes in mechanical behavior. These trends are not even qualitatively correlated with estimates of the excess volume changes associated with addition of the diluents to polysulfone.     

Influence of specimen thickness on isothermal crystallization kinetics. A theoretical analysis

In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.     

Kinetics of re‐embrittlement of (anti)plasticized glassy polymers after mechanical rejuvenation

Mechanical rejuvenation is known to dramatically alter the deformation behavior of amorphous polymers. Polystyrene (PS)—for example, typically known as a brittle polymer—can be rendered ductile by this treatment, while a ductile polymer like polycarbonate (PC) shows no necking anymore and deforms homogeneously in tensile deformation. The effects are only of temporary nature, as because of physical aging the increasing yield stress, accompanied by intrinsic strain softening, renders PS brittle after a few hours, while for PC necking in tensile testing returns in a few months after the mechanical rejuvenation treatment. In this study, it is found that physical aging upon rejuvenation in both PS and PC can be delayed in two different ways: (1) by reducing the molecular mobility through antiplasticization and (2) by applying toughening agents (rubbery core–shell particles). For the first route, even though progressive aging is found to decrease with increasing amounts of antiplasticizer added, dilution of the entanglement network results in enhanced brittleness. Besides antiplasticization effects, also some typical plasticization effects are observed, like a reduction in matrix T_g. For the second route, traditional rubber toughening using acrylate core–shell modifiers also results in a reduced yield stress recovery, and ductile tensile deformation behavior is observed even 42 months after mechanical rejuvenation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 134–147, 2008     

Effect of antiplasticization on gas sorption and transport. II. Poly(phenylene oxide)

The propensity for various diluents to cause antiplasticization of poly(phenylene oxide) was examined and compared with similar responses for polysufone. Of the diluents used, none resulted in significant stiffening of poly(phenylene oxide) at 35°C relative to what was observed for polysulfone in an earlier paper. However, these diluents did cause substantial reduction in gas sorption levels and permeability coefficients. The latter is consequently a more sensitive indicator of changes in molecular motions of glassy polymers caused by diluents. The permeability response of adding low molecular weight diluents is compared with that of adding a high molecular weight polymer, polystyrene, to poly(phenylene oxide). The data were analyzed and interpreted along lines used in the companion paper for polysulfone.     

Interactions of hydrophilic plasticizer molecules with amorphous starch biopolymer—an investigation into the glass transition and the water activity behavior

In this article, we demonstrated that within a hydrophilic biopolymer–plasticizer system, the molecular “activity” of the plasticizer also influenced the extent of these interactions. We demonstrated through an analysis of crystallinity and calorimetry results that the equilibrium moisture content within the starch matrix can preferentially interact with the hydrophilic plasticizers and modify the polymer recrystallization process to an extent that the commonly acknowledged relationship between the crystallinity and the glass transition behavior is disrupted. Two plasticizers, glycerol (three ? OH groups) and xylitol (five ? OH groups), were selected. The water sorption isotherm of polymer samples with 5–20 wt % (dry basis) plasticizers were examined across a water activity range from ～0.11 to ～0.95 and using Guggenheim‐Anderson‐de Boer analysis, we compared the molar sorption enthalpies of various starch–plasticizer mixtures. Finally, the competitive plasticization between water and plasticizer molecules at different water activities was also discussed using known glass transition models. The analyses validated the antiplasticization limit for glycerol to be ～10–15 wt %, but for xylitol, its antiplasticization behavior did not manifest till 20 wt %. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Positron annihilation spectroscopy study of moisture absorption in protective epoxy coatings

Position annihilation spectroscopy (PAS) was used to measure the relative free-volume fraction of protective epoxy coatings before and after exposure to liquid water at room temperature. The relative free volume fraction determined before water exposure was compared to the equilibrium water uptake of each coating and a correlation was found. The relative free-volume fraction of the epoxy coatings decreased slightly after water exposure. This decrease is contrary to the free volume theory of plasticization, but is consistent with the antiplasticization process. Larger decreases in the relative free volume fraction were sought by repeating the water uptake experiments with nitrobenzene which in the bulk, liquid form quenches ortho-positronium (o-Ps). Since the o-Ps lifetime remained approximately constant and the o-Ps intensity decreased after nitrobenzene absorption, nitrcbenzene is believed to be inhibiting the formation of o-Ps in the epoxy free volume cavities. Larger decreases in the relative free volume fractions were found after nitrobenzene exposure than after water exposure. These larger decreases are due to the fact that nitrobenzene is a better inhibitor of o-Ps formation than water in the epoxy free volume cavities. Larger volume fractions of nitrobenzene were absorbed by the coatings than water and were interpreted to be due to interactions between nitrobenzene and the epoxies. © 1993 John Wiley & Sons, Inc.     

Concentration effects in gel permeation chromatography : IV. Contribution of viscosity phenomena and macromolecular expansion

The changes in elution volumes with the changes in the concentration of an injected polymer solution are caused by several contributing effects. Under model conditions, it is possible to assume only the effect of a viscosity gradient in a zone moving along the column and the effect of the concentration dependence of the hydrodynamic volume of a macromolecular coil. The non-Gaussian shape of the zone and the dependence of the width of the elution curve on concentration are factors that complicate the theoretical treatment of concentration effects. The described physico-chemical model allows to evaluate the ratio of mentioned two contributions in the concentration dependence of elution volumes. According to this model, the contribution of the concentration dependence of the hydrodynamic volume does not exceed about 20% of the total change in elution volume with the varying concentration under real experimental conditions. The efficiency of the columns used and the total injected volume of the polymer solution affect this ratio only negligibly. It is obvious from a comparison with earlier results that these conclusions are not fundamentally changed even by the revised model of the concentration dependence of the swelling factor.     

Isoelectric focusing field-flow fractionation IV. Investigations on protein separations in the trapezoidal cross-section channel

The first separation of three proteins (horse spleen ferritin, equine myoglobin and horse heart cytochrome c) by isoelectric focusing field-flow fractionation in a trapezoidal cross-section channel of 0.875 ml volume and 25 cm length is reported. Separation and elution are shown to proceed within about 1 h at a power application of about 1 W. The separation of the three proteins is demonstrated to be dependent on applied electric power, carrier ampholyte concentration and the concentrations of anolyte and catholyte. It follows from these data that the resolution is improved with increasing carrier ampholyte concentration and/or decreasing concentrations of the electrode solutions. The experimentally observed effects are in agreement with predictions made by computer simulation.     

Characterization of the influence of displacing salts on retention in gradient elution ion-exchange chromatography of proteins and peptides.

It has been shown earlier that the choice of displacing salt has a large effect on the retention in ion-exchange chromatography of proteins and peptides. The influence of different displacing salts cannot be predicted or quantitatively explained, owing to the current lack of an adequate theoretical framework. In this work a general characterization is made by using a considerable number of proteins and peptides and all displacing salts found feasible. Principal component analysis is used to interpret the large amount of data that is generated. The results of the analysis indicate that most of the retention variations are due to non-specific effects and can be explained by changes in the apparent gradient slope, i.e., the increase in elution strength per unit volume, and the elution strength of the starting buffer. This differs from the interpretation given earlier, where the selectivity changes were attributed to specific effects of the salts. However, as it is impossible to test all existing proteins and peptides, specific effects are still possible, but they might be less common than previously considered.     

Scattering of light by deformed disordered spherulites

The change in the light-scattering patterns upon deforming two-dimensional disordered spherulites is shown to arise from four effects occurring upon stretching: (1) the change in shape of the spherulite, (2) the change in average orientation of the optic axes of the scattering volume elements, (3) the change in deviation of the optic axis orientation angle from its average value, and (4) the change in the distance over which this deviation is correlated. The effects of these contributions upon the experimental scattering patterns are analyzed.     

Dynamical and statistical effects of the intrinsic curvature of internal space of molecules

The Hamilton dynamics of a molecule in a translationally and/or rotationally symmetric field is kept rigorously constrained in its phase space. The relevant dynamical laws should therefore be extracted from these constrained motions. An internal space that is induced by a projection of such a limited phase space onto configuration space is an intrinsically curved space even for a system of zero total angular momentum. In this paper we discuss the general effects of this curvedness on dynamics and structures of molecules in such a manner that is invariant with respect to the selection of coordinates. It is shown that the regular coordinate originally defined by Riemann is particularly useful to expose the curvature correction to the dynamics and statistical properties of molecules. These effects are significant both qualitatively and quantitatively and are studied in two aspects. One is the direct effect on dynamics: A trajectory receives a Lorentz-like force from the curved space as though it was placed in a magnetic field. The well-known problem of the trapping phenomenon at the transition state is analyzed from this point of view. By showing that the trapping force is explicitly described in terms of the curvature of the internal space, we clarify that the physical origin of the trapped motion is indeed originated from the curvature of the internal space and hence is not dependent of the selection of coordinate system. The other aspect is the effect of phase space volume arising from the curvedness: We formulate a general expression of the curvature correction of the classical density of states and extract its physical significance in the molecular geometry along with reaction rate in terms of the scalar curvature and volume loss (gain) due to the curvature. The transition state theory is reformulated from this point of view and it is applied to the structural transition of linear chain molecules in the so-called dihedral angle model. It is shown that the curvature effect becomes large roughly linearly with the size of molecule.     

Surface Plasticization of Poly(ether ether ketone)

This paper describes a study of the surface plasticization and antiplasticization of an amorphous and a semicrystalline poly(ether ether ketone) (PEEK) in solvent environments using nanohardness method. A range of solvents (octane, chloroform, tetrachloroethane, acetone, dichlorobenzene, polyethyleneglycol (PEG), methanol and water) based on the Hilderbrand’s Solubility Parameter were selected as solvent environments. The results of the nanoindentation hardness experiments performed on the virgin and the solvent immersed polymeric surfaces are reported. The surface plasticization or antiplasticization is reported on the basis of the softening or the hardening of the near surface layers (?1 μm) after immersion of the polymeric surfaces in the solvent environments. Surface plasticization of the amorphous PEEK has been observed in organic solvents. The chlorine containing solvents have severely degraded the hardness of the amorphous polymer. A surface hardening of the amorphous PEEK has been observed after immersion in water. Semicrystalline PEEK was seen to exhibit a considerable inert behaviour to common organic solvents but chlorinated organic solvents and water have caused a decrease in the surface mechanical properties.     

Total versus effective total efficiency in the computation of coincidence summing corrections in gamma-ray spectrometry of volume sources

For the evaluation of coincidence summing effects for volume sources an effective total efficiency (ETE) is used instead of the common total efficiency (TE). In this paper ETE is computed by the Monte Carlo method. The differences between ETE and TE are analyzed and their origin is discussed. Measured values for the coincidence summing correction factors for a standard solution containing ¹⁵²Eu in a one liter Marinelli beaker are compared with computed values obtained from appropriate values of ETE. It is shown that the procedure for the evaluation of the coincidence effects is reliable. As a consequence it can be concluded that ¹⁵²Eu volume sources can be successfully used for efficiency calibration even in the case of high-efficiency detectors and close source-to-detector distances.     

Reduced stress‐optical coefficient of polycarbonate by antiplasticization

We have investigated the effect of antiplasticization on the stress‐optical behavior of polycarbonate (PC) containing terphenyls (tPh) and di(2‐ethylhexyl)adipate (DEHA). Addition of the three tPhs (p‐, o‐, and m‐tPh) and DEHA at contents of 5–10 wt % increases the tensile storage modulus (E' ) of PC owing to the antiplasticization effect. In particular, p‐tPh increases E' more than the other additives, suggesting that the rod‐like shape matches the free volume of PC in the glassy state. The three tPh isomers improve the glassy birefringence of PC while DEHA does not change the glassy birefringence, which corresponds to the polarizability anisotropy. The stress‐optical coefficient, a ratio of stress and birefringence, of PC decreases with increasing additive content in order of p‐tPh ? o‐tPh > m‐tPh = DEHA. This result is agreement with a restricted rotational motion of additive molecule in PC, which is observed in dynamic mechanical and birefringence data. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1837–1842     

Localized volume deficiencies as an effect of spherulite growth. I. The two-dimensional case

Two-dimensional spherulite growth leads to the encirclement of regions of molten polymer in a polymer film. On further crystallization localized volume defects arise, resulting in thin spots in the film. Since this effect lowers the mechanical strength of films, we call these volume defects “weak spots.” A computer program is developed to evaluate the number, size, and shape of such volume defects for athermal, thermal, and mixed modes of primary nucleation of spherulites. It is shown that the total area of weak spots exceeds 10% of the sample area for all types of nucleation studied. The largest weak spots arise in samples crystallized via athermal and mixed nucleation; their size is of the same order as that of an average spherulite. Formation of weak spots is observed in thin films of poly(ethylene oxide) and poly(methylene oxide). The disadvantageous role of weak spots is confirmed by observation of electric breakdown occurring preferentially in weak spots in polypropylene films.     

Quantitative comparisons using liquid chromatography with dual-label radioactivity measurements for evaluation of isotope and impurity effects

Dual-label methods with radiometric measurements with liquid chromatography are evaluated for assessing effects of impurities and isotopic composition in reaction experiments. The procedure is suitably sensitive to detect interferences caused by effects of impurities in reactants, isotope exchange during reaction and effects of kinetic differences due to differing masses of the differently labeled forms. The methods show marked improvements in data quality for comparisons of product formations and relative product abundances in multiple-pathway reaction systems. The results from computer simulations for the procedures are shown to be relatively unaffected by large variations in uncertainties in pretreatment steps and volume measurements. Moreover, these methods yield much better quantitative results than do commonly used corresponding conventional comparisons, and the benefits are corroborated by results from experiments with microsomal reactions.     

Low-energy interactions in high-performance liquid chromatography

Liquid chromatographic systems with very weak excessive analyte-adsorbent interactions have been studied. These systems consisted of a homologous series of n-alkanes as both analytes and mobile phases with a C18 reversed-phase adsorbent. A linear decrease of the analyte retention volume with an increase of the number of analyte carbon atoms was found. Corresponding increases of analyte retention with an increase in the number of eluent carbon atoms was also discovered. An explanation of these two effects on the basis of adsorption theory is proposed. A good correlation of column hold-up volume calculated by interpolation of the retention dependencies for above mentioned systems with that measured by the minor disturbance method has been shown. A study of the temperature dependencies of these alkane systems has shown entropy-governed retention dependencies.     

Diffusivity of gases and main-chain cooperative motions in plasticized poly(vinyl chloride)

Permeability and time-lag measurements for H₂ and CO in poly(vinyl chloride) (PVC) plasticized with tricresyl phosphate show that the apparent diffusion coefficients at first decrease as the plas-ticizer concentration is increased. The diffusion coefficients then increase as the additive concentration is raised above 15 wt %. These changes in the apparent diffusion coefficients can be related to the behavior of a variety of mechanical properties and are attributed to antiplasticization and plasticization effects of low and high concentrations of tricresyl phosphate, respectively. The antiplasticization-plasticization effects reflect altered molecular motions of the polymer. Carbon-13 NMR rotating-frame relaxation rate measurements show directly that the cooperative main-chain molecular motions of PVC are reduced when the additive acts as an antiplasticizer and are increased when the polymer is plasticized. Both the apparent diffusion coefficient and the rotating-frame relaxation rate have a similar dependence on additive concentration. An application of the molecular theory of diffusion of Pace and Datyner accounts qualitatively for the way in which additives alter the average chain interaction energy, cooperative polymer main-chain motions, and the diffusion coefficients of gaseous penetrants.