Effect of water sorption on oxygen‐barrier properties of aromatic polyamides

Aromatic polyamides based on poly(m‐xylylene adipamide) (MXD‐based polyamides) and poly(hexamethylene isophthalamide) (HMD‐based polyamides) were examined. Insight into the excellent gas‐barrier properties was obtained by the characterization of the effect of water sorption on the thermal transitions, density, refractive index, free‐volume hole size, and oxygen‐transport properties. Reversing the carbonyl position with respect to the amide nitrogen substantially lowered the oxygen permeability of MXD‐based polyamides in comparison with that of HMD‐based polyamides by facilitating hydrogen‐bond formation. The resulting restriction of conformational changes and segmental motions reduced diffusivity. The primary effect of water sorption was a decrease in the glass‐transition temperature (T_g) attributed to plasticization by bound water. No evidence was found to support the idea that sorbed water filled holes of free volume. When the polymer was in the glassy state, the drop in T_g accounted for hydration‐dependent changes in the density, refractive index, and free‐volume hole size. The correlation of the oxygen solubility with T_g and density confirmed the concept of oxygen sorption as filling holes of excess free volume. In some cases, water sorption produced a glass‐to‐rubber transition. The onset of rubbery behavior was associated with a minimum in the oxygen permeability. The glass‐to‐rubber transition also facilitated the crystallization of MXD‐based polymers, which complicated the interpretation of oxygen‐transport behavior at higher relative humidity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1365–1381, 2005     

Effects of organophilic montmorillonite on hydrogen bonding, free volume and glass transition temperature of epoxy resin/polyurethane interpenetrating polymer networks

Epoxy resin nanocomposites containing organophilic montmorillonite (oM) and polyurethane were prepared by adding oM to interpenetrating polymer networks (IPNs) of epoxy resin and polyurethane (EP/PU). The dispersion degree of oM in EP/PU matrix was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fourier transform infrared spectrometry (FT-IR) showed that strong interactions existed between oM and EP/PU matrix, and oM had some effect on hydrogen bonding of these EP/PU IPNs nanocomposites. Positron annihilation spectroscopy (PALS) and differential scanning calorimetry (DSC) measurements were used to investigate the effect of oM and PU contents on free volume and glass transition temperature (T_g) of these nanocomposites. The PALS and DSC results clearly showed that the presence of oM led to a decrease in the total fractional free volume, which was consistent with increasing T_g upon addition of oM, ascribed to increasing hydrogen bonding in interfacial regions of oM and EP/PU matrix and enhancing the miscibility between EP phase and PU phase. In addition, with increasing PU content, the total fractional free volume increased, corresponding to decreasing T_g.     

An application of an homogenization method to a model of diffusion in glassy polymers

The sorption of gases in polymers below their glass-transition temperature T_g is known in many cases to be described by the “dual sorption” theory, according to which the gas is held in accordance with both the Langmuir and Henry's laws. Based on this theory, expressions for the “effective diffusion coefficient” in the glassy polymers have been obtained by investigators in the past, notably by Paul and Koros.² The present analysis regards the glassy polymers as inhomogeneous with regions on which the gas sorption follows the Langmuir law. Assuming that the linear dimensions of these regions, which are often referred to as “microvoids” (although they are not space filled by vacuum), are small compared to the macroscopic length of interest but large compared to the mean free path of the penetrant gas molecules, we derive a rigorous relation between the average flux and the concentration gradient in the polymer and show that this relation can be expressed in terms of an “effective diffusion coefficient” D_eff which depends on the details of the microstructure, i.e., the size, shape and spatial distribution of the “microvoids.” This expression for D_eff is shown to reduce to that of Paul and Koros² in two situations: (1) when the “voids” consist of slabs running parallel to the concentration gradient, and (2) when the “voids” are spherical and the temperature of the polymer is not too different from T_g. The results of the present study lead to an alternative procedure for interpreting the experimental data on sorption and permeation which may have some advantages over the procedure currently employed. Finally, the analysis presented here is also applicable to polymers containing adsorptive fillers.     

Soluble polybenzimidazoles with intrinsic porosity: Synthesis,structure, properties and processability

We have explored two novel comonomers, namely, 4,16‐dicarboxyl[2.2]paracyclophane and 5,5′,6,6′‐tetraamino‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobi[indane], for the synthesis of co‐polybenzimidazoles (co‐PBIs) with intrinsic porosity. Both these monomers possess twisted structures that can lead to “awkward” macromolecular shapes that cannot pack efficiently. The consequences of introducing these two monomers on the structure and properties of PBIs are reported. The random copolymers synthesized are amorphous and possess glass transition temperatures (T_gs) greater than 400 °C. T_g decreases with increasing comonomer content indicating an increase in fractional free volume. The copolymers have low surface area. TEM and BET measurements show evidence of mesopore formation. The copolymers show significant carbon dioxide adsorption. Single chain molecular dynamics simulation of 24‐mer repeat units shows intramolecular void spaces arising as a result of distorted polymer chain with reduced conformational mobility. These studies define a new synthetic strategy for “bottoms‐up” synthesis of PBIs with intrinsic porosity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1046–1057     

“Vanishing” structural effects of temperature in polymer glasses close to the glass-transition temperature

Positron annihilation lifetime (PAL) measurements were used for observation of structural effects of temperature in polystyrene (PS), super-cross-linked polystyrene networks (CPS), and in polyimides (PI) below and in the vicinity of glass-transition temperature T_g. “Vanishing” of these structural effects in the repeating cycles of the temperature controlled PAL experiments due to the slow relaxation processes in different conditions and details of chemical structure is demonstrated. Obtained results illustrate complex, dependent on thermal history, inhomogeneous character of the glass structure. In fact, structure of some polymer glasses is changing continuously. Calculations of the number density of free volume holes in these conditions are discussed.     

Positronium annihilation in amine-cured epoxy polymers

Positronium annihilation spectroscopy (PAS) has been used to study the microstructural properties of amine-cured epoxy polymers. We have determined the free-volume “hole” sizes in these polymers by comparing the observed ortho-positronium lifetimes with the known lifetime–free volume correlation for low-molecular-weight systems. The free volumes for four epoxies with different crosslink densities are found to vary significantly over the temperature range between ?78° and 250°C. The free-volume holes for these polymers are found to range from 0.025 to 0.220 nm³. Two important transition temperatures were found: one corresponds to the glass transition temperature T_g determined by differential scanning calorimetry (DSC), and the other occurs about 80–130°C below T_g. The sub-T_g transition temperature is interpreted tentatively as being where hole size reaches dimensions adequate for positronium trapping or else the onset temperature for local mode or side-chain motions. These two transition temperatures plus two additional onset temperatures are found to be correlated with crosslink densities calculated from stoichiometry.     

H2 adsorption by noble gas insertion compounds: A computational study

In order to find a solution of energy-related problems, sophisticated hydrogen storing materials are needed as hydrogen is an abundant and environment friendly fuel. We have investigated the hydrogen storage potential of Ng inserted metal acetylide and metal cyanide compounds (metal ​= ​Cu, Ag and Au) at the ωB97X-D/cc-pVTZ-PP level of theory. Due to the difference in electronegativity and formal charge on metal atoms in the insertion compounds, the interaction with the hydrogen molecule is expected to be different. The adsorption energies, the free energy of adsorption, natural charges on atomic centers/moieties are obtained through the natural population analysis, and energy decomposition analysis has also been carried out for nH₂···MNgCCH and nH₂···MNgCN (n ​= ​1–3). The hydrogen adsorption capacity of the strongest and the weakest cases has also been investigated. Both the insertion compounds, MNgCCH and MNgCN, are found to adsorb a maximum of three hydrogen molecules on the metal site. The single H₂ adsorbed minimum energy structures of studied compounds show a “T-shaped” orientation while double H₂ adsorbed minimum energy structures are of “Y- shaped” geometry and those of tricoordinated structures resemble “T_d-like” shape. The negative value of Gibbs free energy change suggests the thermodynamical spontaneity of the hydrogen adsorption process.     

Use of blowing catalysts for integral skin polyurethane applications in a controlled molecular architectural environment: Synthesis and impact on ultimate physical properties

Polyurethane elastomers of a controlled molecular architecture were synthesized using a two‐step polymerization technique. The building blocks of the elastomeric materials included urea–urethane prepolymers end‐capped with diisocyanate groups and had an exact number of urea groups at both ends. Two‐dimensional bifurcated hydrogen‐bonding networks incorporating the urea groups were, with differential scanning calorimetric and dynamic mechanical thermal analyzer techniques, responsible for the increase in the glass‐transition temperature (T_g) of the hard block and sharp interface morphology between the pure “hard” domains and pure “soft” domains. The higher extent of the phase separation between the two phases contributed to higher elastic moduli for the hard blocks and higher tensile strength for the elastomeric samples. Higher elongation values were attributed to the liberation of the elastomeric chain ends that otherwise would have been constrained in the interface region. The higher T_g values of the hard blocks corresponded to an increase in the hardness values and a decrease in the tear‐strength values. The increase in the amount of urea groups within the hard segments, as a result of the increased amount of water and blowing catalyst, resulted in elastomeric foams with higher open‐cell content. This resulted in lower resilience values as measured using the pendulum rebound test and was attributed to the ability of the open cells to absorb and dissipate energy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2526–2536, 2002     

Sorption of water vapor by poly(vinyl acetate)

Summary The sorption property of water vapor by poly(vinyl acetate) (PVAc) of relatively low glass transition temperature (T _g) was studied at temperatures nearT _g.Tc_g of humidity-controlled samples of various moisture contents was measured and its variation with the moisture content was determined.T _g of the dry sample was estimated by dilatometry and DSC methods, and to confirm the value, the temperature dependence of mutual diffusion coefficient of the system of water vapor + PVAc was determined. A difference between the sorption mechanisms of water vapor by PVAc at 20 and 30 °C was observed: two sorption mechanisms are involved at 30 °C, while three mechanisms at 20 °C are involved which include the above two and another intermediate one. In earlier stage of sorption, at both 20 and 30 °C, water molecules sorbed by PVAc showed a tendency towards aggregation, while a mixing effect was found at higher stage of the sorption.

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Zusammenfassung In der Arbeit werden Wasserdampfsorptionseigenschaften von Polyvinylacetat mit relativ niedriger Glastemperatur (T _g) in der Nähe vonT _g untersucht. Es wurden Plastizitätseinflüsse und Veränderungen vonT _g mit dem Wassergehalt studiert. Es wurde gefunden, daß bei 30 °C ein 2-Stufen-Sorptionsmechanismus, bei 20 °C ein 3-Stufen-Mechanismus existiert.

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With 7 figures     

Moisture transport studies on newly developed aromatic and aromatic/aliphatic copolyester thin films

In polymers for microelectronics applications, moisture is known to have a deleterious effect upon device reliability. In this paper, the moisture transport behaviors of a newly developed family of all-aromatic and aromatic/aliphatic copolyester thermosetting films were described. The moisture uptake as a function of temperature, relative humidity, sample thickness, and processing conditions were presented via conjugate moisture sorption tests.¹ It was found that the post curing near but below T_g resulted in an increase in both total moisture uptake and diffusion coefficient due to the effect of physical aging and the generation of sample defect volume. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1025–1035, 1998     

Analysis of the melt viscosity and glass transition of polystyrene

The melt viscosity, the glass transition, and the effect of pressure on these are analyzed for polystyrene on the basis of the Tammann-Hesse viscosity equation: log η = log A + B/(T ? T₀). Evidence that the glass transition is an isoviscosity state (log η_g ? 13) for lower molecular weight fractions (M < M_c) is reviewed. For a polystyrene fraction of intermediate molecular weight (M ? 19,000; t_g = 89°C.), it is shown that B is independent of the p–v–T state of the polymer liquid and that dT₀/dP = dT_g/dP. This is consistent with the postulate that B is determined by the internal barriers to rotation in the isolated polymer chain. Relationships are derived for flow “activation energies” at constant pressure and at constant volume, and for the “activation volume.” Values for polystyrene along the zero-pressure isobar and along the constant viscosity, glasstransition line are reported. For the latter, ΔV_g* is constant and corresponds to about 10 styrene units. The “free volume” viscosity equation: log η = log A + b/2.3?, is reexamined. For polystyrene and polyisobutylene, ?_g/b = 0.03, but ?_g and b themselves differ appreciably in these polymers. The parameter b is the product of an equilibrium term Δα and the kinetic term B, and none of these is a “universal” constant for different polymers. The physical significance of the free volume parameter ?, particularly with regard to the “excess” liquid volume, remains undefined. Two new relationships for dT_g/dP, one an exact derivation and the other an empirical correlation, are presented.     

Interaction of inorganic salts with polar polymers. I. Physical properties of phenoxy–calcium thiocyanate mixtures

Calcium thiocyanate is appreciably soluble in “Phenoxy” polymer. Solutions of this salt have significantly different physical properties compared to the pure polymer. The glass-transition temperature T_g is increased, and the kinetics of the glass transition are affected. The melt viscosity and its temperature dependence are increased. The viscosity changes are predicted from the changes in T_g and thermal expansion coefficients, in contrast to ionomers, in which clustering or domain formation cause viscosity to increase. Mechanical properties of the glassy polymers are also affected by the presence of dissolved salt. The most striking effect is an increased resistance to stress cracking by polar organic liquids. This may be related to the T_g increase, or to changes in solubility parameter, as indicated by insolubility of the salt solutions in solvents for the pure polymer. Increased water sorption and electrical conductivity are also results of salt incorporation.     

Glass transition in the lower homologues of polyethyleneoxide

Experimental measurements of T_g for two series of lower homologues of polyethyleneoxide. differing in their end-groups, are discussed in terms of existing theories. Simple free-volume considerations predicting linear dependence of T_g on (molecular weight)^?1 are inadequate in systems with end-groups capable of specific interactions (hydrogen bonding). Thermodynamic arguments show that the true T_g of infinitely long PEO chain is 220 ± 5°K. Suitable modification of parameters of the Gibbs-DiMarzio equations to account for the dependence of the free volume fraction on the concentration of end-groups results in good fit of the experimental data for hydroxyl-terminated samples and correctly predicts T_g(∞). Analysis of the data for chlorine-substituted oligomers suggests the existence of specific intermolecular interactions in the latter, involving chlorine atoms.     

Moisture absorption and diffusion in an underfill encapsulant at T > T g and T < T g

Moisture absorption and diffusion behavior of an underfill material used for electronic packaging with a glass transition temperature (T _g) slightly above room temperature have been investigated by the sorption thermogravimetric analysis technique. It has been found that moisture diffusion in this material follows the Fick’s diffusion model, and moisture absorption–desorption is reversible and repeatable. Based on moisture-induced mass gain versus time curve, the diffusion constant can be determined. It was found that below T _g, moisture diffusivity exhibits an Arrhenius temperature dependence, which changes to a different Arrhenius temperature dependence as the temperature increases to T > T _g. The change in diffusivity from T < T _g to T > T _g is accompanied by a significant decrease in the energy barrier for moisture diffusion. Results shed light on the change in moisture diffusion in polymer-based materials in the glassy and the rubbery state.     

Thermal characterizations of multifunctional epoxy/anhydride systems used for pultruded composite ropes

The viscoelastic characterization and thermal stability property of some multifunctional epoxy/anhydride systems cured at different schedules were investigated by dynamic mechanical thermal analysis (DMTA) in single cantilever mode at fixed frequency, and by non-isothermal thermogravimetric (TG) analysis, respectively. According to the DMTA results, three obviously different glass transition temperatures (T _g), were observed, among which TGDDM/MHHPA system exhibits the largest T _g. While from the TG curves, the results of the mass loss and thermal stability showed that, after cured for a prolonged duration, the TGDDM/MHHPA system possessed the most excellent performance in heat resistance.     

Isotope effect in gas transport. II. Effect of the glass transition on the size of the free volume element

A diffusive gas-transport isotope effect is used to estimate the size of the free volume element above and below the glass transition for poly(ethyl methacrylate) and poly(vinyl fluoride). The cavity size, as measured by the hydrogen probe molecule, is apparently larger in the glassy region for both polymers than it is above T_g. It is postulated that the number of free volume elements essentially decreases below T_g, so that the total free volume, which is the sum of all such elements, is smaller below the glass transition, in accord with density measurements on bulk polymers.     

The effects of molecular orientation on the physical aging and mobility of polycarbonate—solid state NMR and dynamic mechanical analysis

Solid‐state NMR and dynamic mechanical (DMA) measurements were performed on a series of uniaxially hot‐drawn bisphenol‐A polycarbonate samples in order to determine the effects of stretching on the structure, mobility, and local orientation environment. Proton spin‐lattice relaxation times, ¹H T_1ρ, for the phenylene carbon protons were fitted to a biexponential decay function, and both the long and short relaxation times initially increased with stretching. Intensity data indicated an increase in the number of short relaxation time protons and a decrease in the number of long relaxation protons with orientation. Similarly, DMA spectra showed that the β‐relaxation strength also increased with drawing, which implied an increase in the number of localized segmental relaxations. It is theorized that the long and short ¹H T_1ρ relate to protons within tightly packed “cooperative domains,” and to those with greater localized free‐volume, respectively. Stretching is known to distort the free‐volume distribution, causing a decrease in the mean free‐volume but an increase in the number of larger, more elliptical holes. This is expected to cause a decrease in the α‐transition mobility (due to larger cooperative domains) and an increase in the β‐mobility (due to the increase in the number of β‐relaxing segments associated with the larger free‐volume holes). These predictions are consistent with results recently reported by Shelby and Wilkes on the physical aging and creep behavior of these samples (M. D. Shelby & G. L. Wilkes, Polymer 1998, 39, 6767; M. D. Shelby & G. L. Wilkes, J Polym Sci Part B: Polym Phys 1998, 36, 2111). © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 32–46, 2001     

Positron annihilation lifetime and differential scanning calorimetric study of immiscible NBR/PE blends

The temperature dependence of the mean size of nanoscale free‐volume holes, 〈V_h〉, in polymer blend system consisting of polar and nonpolar polymers has been investigated. The positron lifetime spectra were measured for a series of polymer blends between polyethylene (PE) and nitrile butadiene rubber (NBR) as a function of temperature from 100 to 300 K. The glass transition temperatures (T_g) for blends were determined from the ortho‐positronium (o‐Ps) lifetime τ₃ and the mean size of free‐volume holes 〈V_h〉 versus temperature as a function of wt % of NBR. The T_gs estimated from the PALS data agree very well with those estimated from DSC in view of different time scales involved in the two measurements. Both DSC and PALS results for the blends showed two clear T_gs of a two‐phase system. Furthermore, from the variation of thermal expansivity of the nanoscale free‐volume holes, the thermal expansion coefficients of glass and amorphous phases were estimated. Variations of the o‐Ps formation probability I₃ versus temperature for pure PE and blends with low wt % of NBR were interpreted on the basis of the spur reaction model of Ps formation with reference to the effects of localized electrons and trapping centers produced by positron irradiation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 227–238, 2009