Study of thermal annealing on Matrimid fiber performance in pervaporation of acetic acid and water mixtures

Unlike the case for low-sorbing gas molecules such as N₂ and O₂, Matrimid^® hollow fibers swell significantly in acetic acid (HAc) and water mixtures. Acetic acid was found to plasticize the polymer and facilitate the passage of the ‘slow’ molecule, acetic acid, while not affecting the ‘fast’ molecule, water, as significantly. The membrane selectivity of water over HAc inevitably decreased with increasing HAc content in the feed for the standard membrane. Sub-T_g (glass transition temperature) thermal annealing was used to stabilize large bore size defect-free Matrimid^® hollow fibers by suppressing the HAc-induced plasticization. The resulting membrane selectivity was increased up to 95 using a 520 μm outer diameter/325 μm inner diameter and 20 cm long defect-free annealed fiber with acceptable water flux (1.6 kg/m² h) for 20 wt% HAc concentration feed streams at 101.5 °C. Micro-fluorescence spectra provide strong support for the notion that thermal annealing can reduce the free volume and promote the formation of charge transfer complexes. As a consequence, the improved rigidity of the polymer chains increases the polymer discrimination of shape and size for penetrants, although no chemical reaction occurs with thermal annealing.     

Sorption and transport of methanol in poly(ethylene terephthalate)

This paper reports the sorption and diffusion characteristics of methanol vapor in polyethylene terephthalate (PET). Amorphous PET, semicrystalline, biaxially oriented annealed and non-annealed samples have been studied for equilibrium sorption and kinetics of methanol. At activities of methanol less than 0.30, uptake shows Fickian kinetics and isotherm follows the Dual Mode model. Diffusion coefficients increase with penetrant concentration and are of the order of 10⁻¹⁰ cm²/s. Hysteresis during desorption and increase in solubility during resorption suggest methanol induced conditioning effects which may have detrimental effects on the barrier efficacy of PET. At activities greater than 0.30, swelling and relaxation effects occur and the isotherms show Flory-Huggins behavior for all three samples. Uptake follows two-stage kinetics fit by the Berens-Hopfenberg model. Greater polymer chain stability due to annealing reduces the extent of relaxation and improves the barrier efficacy over amorphous and non-annealed, oriented PET. For amorphous PET, at 80% activity and above, an induction time is observed which is absent in the semicrystalline films, suggesting strong relaxation effects in the amorphous phase of PET.     

Sorption and transport of linear and branched ketones in biaxially oriented polyethylene terephthalate

Equilibrium sorption and kinetics of acetone, methyl ethyl ketone (MEK), methyl n-propyl ketone (MnPK), and methyl i-propyl ketone (MiPK) uptake in uniform, biaxially oriented, semicrystalline polyethylene terephthalate films were determined at 35 °C and low penetrant activity. Sorption isotherms for all penetrants were well described by the dual-mode sorption model. Sorption and desorption kinetics were described either by Fickian diffusion or a two-stage model incorporating Fickian diffusion at short times and protracted polymer structural relaxation at long times. Diffusion coefficients and equilibrium solubility at fixed relative pressure decreased in the following order: acetone>MEK>MnPK>MiPK. Diffusion coefficients for each penetrant increased with increasing penetrant concentration.     

Miscibility study of Torlon polyamide-imide with Matrimid 5218 polyimide and polybenzimidazole

We have discovered two new miscible polymer blend systems, namely, Torlon^® 4000T with Matrimid^® 5218 and Torlon 4000T with polybenzimidazole (PBI). Both Matrimid 5218 and PBI are miscible at a molecular level with Torlon 4000T over the whole composition range as confirmed by microscopy, DSC, FTIR and DMA. DSC and DMA studies show the existence of a single glass transition in each blend. The T_g-composition curve of Torlon/Matrimid blend system forms a sigmoid curve as a function of composition, while the T_g-composition curve of the Torlon/PBI blend system is double parabola-like. FTIR spectra show the existence of hydrogen-bonding interactions in these two polymer blend systems.     

Anomalous transport of hydrocarbons in polystyrene

The transport kinetics and equilibrium concentrations of n-pentane at high penetrant activities in cast, annealed polystyrene were determined and compared with similar measurements in biaxially-oriented polystyrene. The rate of Case II (relaxation-controlled) sorption in biaxially-oriented polystyrene is three to four times faster than the sorption rate in cast, annealed polystyrene. The Case II sorption process in biaxially-oriented polystyrene is more highly temperature dependent than in cast, annealed film. The higher activation energies coupled with the larger relaxation-controlled sorption rates in biaxially-oriented polystyrene imply the involvement of larger polymer segments in the rate controlling polymer relaxations. The sorption in cast, annealed polystyrene was a position-dependent relaxation controlled transport process; in contrast the sorption in biaxially oriented polystyrene, albeit relaxation-controlled, was not position dependent. The position dependence of the Case II sorption appears to be a consequence of the presence of residual benzene in the film which accelerates the rate-determining relaxations. Desorption measurements at very low penetrant activities were quite similar for both biaxially oriented and cast, annealed polystyrene. The desorption kinetics were Fickian and were only a weak function of polymer orientation at these low activities.     

In situ characterization of moisture sorption/desorption in thin polymer films using optical waveguide spectroscopy

The kinetics of moisture sorption/desorption in poly(terephthalate-co-phosphate) thin films was investigated in situ at T = 25 °C using optical waveguide spectroscopy (OWS). At low water activities, Fickian diffusion was observed for the initial phase of the sorption process, while at high activities, due to the clustering of water, a complex sorption behavior was found. The moisture sorption isotherms were analyzed according to both the Zimm and Lundberg model as well as the Brown model, which suggests the formation of clusters of water molecules in poly(terephthalate-co-phosphate) at water activities of α₁ = 0.58 or higher. The water diffusion coefficient decreases with increasing water activity, which also suggests water cluster formation. A biphasic desorption behavior was also observed upon decreasing the water activity from α₁ = 1 to 0. This study demonstrated the unique advantages of OWS in characterizing in situ the sorption/desorption behavior of penetrants in polymer thin films.     

Drifts in penetrant partial molar volumes in glassy polymers due to physical aging

Sorption and dilation measurements on three different glassy polymer materials are reported to characterize the presence of unrelaxed volume and how it is affected by physical aging. Substantial changes in the sorption and dilation due to physical aging were observed for 25.4 μm thick films of Matrimid^® and Lexan^®, but not significantly for Ultem^®. Such effects are more pronounced when the partial molar volume is considered, since the more aged samples showed less sorptive capacity yet more swelling as compared to their unaged counterparts. Experimentally observed trends in the partial molar volume due to physical aging are qualitatively consistent with trends expected based on the idealized dual mode sorption and dilation models. On the other hand, quantitative discrepancies between expected and observed dilation behaviors reveal some limitations associated with the conventional simple interpretation of the model parameters.     

Preparation and characterization of SAPO-34 – Matrimid 5218 mixed matrix membranes for CO2/CH4 separation

Different SAPO-34 zeolite loaded Matrimid^® 5218 mixed matrix membranes (MMMs) were prepared by solution casting method and characterized using XRD and SEM analysis. Findings showed that semi crystalline neat polymer becomes more crystalline after thermal treatment at higher temperatures close to Matrimid^® 5218 glass transition temperature. Furthermore, incorporation of crystalline filler particles of SAPO-34 zeolite resulted in more and more crystallinity of the MMMs. SEM images also exhibited acceptable contacts between the filler particles and the polymer chains. Permeation measurement showed that CO₂ permeabilities and CO₂/CH₄ selectivities of the MMM with 20 wt% loading of SAPO-34 zeolite particles up to 6.9 (Barrer) and 67, respectively. This can be attributed to size discrimination of SAPO-34 pores that falls between CO₂ and CH₄ kinetic diameters.     

Pure and mixed gas CH4 and n-C4H10 sorption and dilation in poly(1-trimethylsilyl-1-propyne)

Pure and mixed gas n-C₄H₁₀ and CH₄ sorption and dilation in poly(1-trimethylsilyl-1-propyne) (PTMSP) are reported at temperatures ranging from −20 to 35 °C. The presence of n-C₄H₁₀ in the mixture considerably reduces CH₄ solubility. For example, CH₄ solubility (in the limit of zero CH₄ fugacity) at 25°C decreases from 4.0 (pure gas) to 0.78 cm³(STP)/(cm³ polymer atm) in the presence of n-C₄H₁₀ at an activity of 0.60. At −20 °C, CH₄ solubility decreases by almost an order of magnitude, from 10.2 (pure gas) to 1.22 cm³(STP)/(cm³ polymer atm) in the presence of n-C₄H₁₀ at an activity of 0.61. In contrast, n-C₄H₁₀ mixture sorption properties are not measurably affected by the presence of CH₄. The dual mode sorption model parameters for CH₄ and n-C₄H₁₀ in PTMSP were determined from pure and mixed gas sorption measurements, and this model can adequately describe the sorption data. The n-C₄H₁₀/CH₄ mixed gas solubility selectivity in PTMSP decreases as temperature increases and as n-C₄H₁₀ activity increases. For example, at 25 °C, the n-C₄H₁₀/CH₄ solubility selectivity decreases from 250 to 120 as n-C₄H₁₀ activity increases from 0.02 to 0.25. At −20 °C and an n-C₄H₁₀ activity of 0.24, the n-C₄H₁₀/CH₄ solubility selectivity is 590. Penetrant-induced volume dilation of PTMSP can be adequately modeled by assuming that all swelling is caused by penetrant molecules sorbed in the polymer's dense equilibrium region (i.e., the Henry's law region) during sorption. However, the best fit partial molar volumes in the Henry's law region for the dilation data are considerably lower than the penetrant partial molar volumes in liquids, suggesting that further theoretical efforts are needed to develop predictive models of volume dilation in high free volume glassy polymers.     

Structure of an <Emphasis Type="Italic">n</Emphasis>-heptane/toluene flame: Molecular beam mass spectrometry and computer simulation investigations

Molecular beam mass spectrometry was used to measure mole fraction profiles of the reactants, major reaction products and intermediates, including precursors of polycyclic aromatic hydrocarbons, in a premixed fuel-rich (equivalence ratio of 1.75) n-heptane/toluene/O₂/Ar flame stabilized on a flat burner at atmospheric pressure. The ratio of the liquid volumes in the n-heptane/toluene mixture was 7: 3. The chemical structure of the flame was modeled using a detailed mechanism of chemical reactions tested against experimental data of other authors on n-heptane/toluene flames and comprising the reactions of formation of polycyclic aromatic hydrocarbons. The mechanism was extended with cross-reactions involving derivatives of n-heptane and toluene. Overall, the new experimental data are in satisfactory agreement with the numerical simulation results; however, there are differences between the measured and calculated mole fraction profiles of some species. Analysis shows that in the n-heptane/toluene flame, the main reactions leading to the formation of low-aromatic compounds (benzene and phenyl) are reactions typical of the pure toluene flame.     

An investigation of the effects of pyrolysis parameters on gas separation properties of carbon materials

A significant extension of an earlier analysis of molecular sieving carbons formed from polymeric precursors is reported for separation of important gas pairs including O₂/N₂, CO₂/CH₄ and C₃H₆/C₃H₈. Previously, it was shown that changing the time or temperature of the pyrolysis protocol for a commercially available polyimide (Matrimid^®) altered the final properties of the carbons produced. Changing the precursor material was shown in this study to also affect the final carbon material obtained for a given final pyrolysis temperature. Analysis of low temperature carbon dioxide adsorption isotherms using density functional theory was employed to characterize the microporosity of the materials. Results are given here for a totally different packing-inhibited polyimide precursor (6FDA/BPDA-DAM). Sorption, permeation and diffusion data are compared with those obtained using the more densely packed commercial polyimide precursor Matrimid^® studied earlier. Thermal soak was also investigated and the effect on permeation properties determined for carbons using both precursors. The results indicate that carbons from both precursors have size-selective ultramicropores as well as larger nonselective micropores that provide high capacity sorption sites for penetrants. High permselectivities, combined with high permeabilities are found for some of the samples when compared with conventional polymer materials. A hypothetical ultramicropore size distribution is shown to be useful to relate transport data to results from more commonly used characterization techniques such as pore size distribution analysis.     

Infra-red spectrum of the tight (110) fold in n-C198H398

The alkane n-C₁₉₈H₃₉₈ has been crystallised in both extended chain and once-folded forms and annealed to produce materials with low concentrations of gauche bonds. The concentrations of the specific conformers detected by FTIR spectroscopy at −173 °C are calculated, using measurements on liquid n-hexadecane for calibration: values are all generally less than 2.0 per 100 carbon atoms, with extended chain samples showing values less than 1.0 per 100 carbon atoms. A subtraction spectrum (Once-folded chain sample minus Extended chain sample) shows positive bands at 1298, 1340, 1347 and 1369 cm⁻¹, which are predicted in earlier calculations for a (110) fold, while additional positive bands at 1353 and 1363 cm⁻¹ are assigned, respectively, to gg conformers and (tentatively) to strained gtg or gtg′ conformations.     

Precipitation of asphaltenes from solvent-diluted heavy oil and thermodynamic properties of solvent-diluted heavy oil solutions

Ratios of n-heptane (hep) to toluene (tol) affect the solubility of the asphaltenes in heavy oil extraction processes. Consequently phase changes and time after mixing n-heptane and heavy oil in toluene are important for understanding produced emulsions. The kinetics of phase change when n-heptane is added to toluene-diluted heavy oils, and the thermodynamic properties of partially deasphalted heavy oils were studied. The methods used were monitoring precipitation in time using light microscopy, quantitative asphaltenes analysis by near infrared spectroscopy, refractive index and densities measurements, and calculated solubility parameters of mixtures. At critical mass ratios of hep/tol from 1.37 to 2.0 in diluted heavy oil the precipitated asphaltene particles were observed under the microscope after lag times from 2 h to instantly. Lag times were longer at low initial oil concentration. The floc growth time decreased as heavy oil concentration in toluene increased. The growth patterns in time appeared as dots to beads (strings) to clusters (fractal-like flocs). Final wt% precipitated asphaltenes vs. mass fraction (hep+tol)/heavy oil followed sigmoidal relationships. Curves showing wt% soluble asphaltenes vs. mass fraction hep/tol after 24 h initially followed the same shape as time zero curves and diverged at the onset ratios of hep/tol. Slope for precipitated asphaltenes vs. solubility parameters curve showed a break at 16.4 MPa^1/2. Linear correlations were established for concentrations of soluble asphaltenes in residual oils and density, for refractive index and density and for refractive index and solubility parameter. The latter correlation was in accordance with Lorenz-Lorentz theory. These equations provided a means by which oil density, refractive index and solubility parameter can be predicted when these measurements are difficult to measure practically.     

Coupling of mutual diffusion to viscoelasticity in moderately concentrated polyisobutylene solutions

The normalized intensity autocorrelation function g⁽²⁾(t) were obtained by dynamic light scattering for moderately concentrated entangled solutions of polyisobutylene in n-heptane at 25.0 °C and in isoamyl isovalerate (IAIV) at 25.0 °C (Θ). The obtained data have been successfully analyzed by the ‘procedure X’ familiar for determination of mechanical relaxation spectra on the basis of the recent theory for g⁽²⁾(t). The results have shown that while the mutual diffusion coefficient D increases in the n-heptane solutions and decreases in the IAIV solutions with increasing polymer mass concentration c, the friction coefficient ζ for both solutions increases with c showing the same power-law behavior irrespective of the weight-average molecular weight M_w and solvent quality. It has been found that the instantaneous longitudinal modulus L₀ for n-heptane solutions increases in proportion to c², obeying the familiar relation for the plateau value (4/3)G_N of the longitudinal stress relaxation modulus, but L₀ for the IAIV solutions becomes progressively smaller than the values predicted from the relation with decreasing c. The terminal relaxation time τ_m has been found to follow the power-law τ_m∝M_w^3.4 established by rheological measurements.     

Catalytic Hydroprocessing of p-Cresol: Metal, Solvent and Mass-Transfer Effects

A systematic study of the comparative performances of supported Pt, Pd, Ru and conventional CoMo/Al₂O₃, NiMo/Al₂O₃, NiW/Al₂O₃ catalysts as well as the effects of solvent, H₂ pressure and temperature on the hydroprocessing activity of a representative model bio-oil compound (e.g., p-cresol) is presented. With water as solvent, Pt/C catalyst shows the highest activity and selectivity towards hydrocarbons (toluene and methylcyclohexane), followed by Pt/Al₂O₃, Pd and Ru catalysts. Calculations indicate that the reactions in aqueous phase are hindered by mass-transfer limitations at the investigated conditions. In contrast, with supercritical n-heptane as solvent at identical pressure and temperature, the reactant and H₂ are completely miscible and calculations indicate that mass-transfer limitations are eliminated. All the noble metal catalysts (Pt, Pd and Ru) show nearly total conversion but low selectivity to toluene in supercritical n-heptane. Further, conventional CoMo/Al₂O₃, NiMo/Al₂O₃ and NiW/Al₂O₃ catalysts do not show any hydrodeoxygenation activity in water, but in supercritical n-heptane, CoMo/Al₂O₃ shows the highest activity among the tested conventional catalysts with 97?% selectivity to toluene. Systematic parametric investigations with Pt/C and Pt/Al₂O₃ catalysts indicate that with water as the solvent, the reaction occurs in a liquid phase with low H₂ availability (i.e., low H₂ surface coverage) and toluene formation is favored. In supercritical n-heptane with high H₂ availability (i.e., high H₂ surface coverage), the ring hydrogenation pathway is favored leading to the high selectivity to 4-methylcyclohexanol. In addition to differences in H₂ surface coverage, the starkly different selectivities between the two solvents may also be due to the influence of solvent polarity on p-cresol adsorption characteristics.     

A soot formation embedded reduced reaction mechanism for diesel surrogate fuel

A reduced diesel surrogate fuel chemical reaction mechanism of n-heptane/toluene was developed, the reduced mechanism (referred as the “THU mechanism”) includes 60 species and 145 reactions, and it contains soot formation reactions. The THU mechanism was developed from the existing n-heptane/toluene mechanism (70 species and 313 reactions) of Chalmers University of Technology (referred as the “CTH mechanism”). SENKIN and XSENKPLOT were used to analyze the important reactions and species during n-heptane, toluene oxidation and soot formation processes to formulate the reduced mechanism. Ignition delays of n-heptane and toluene predicted by the THU mechanism match well with the CTH mechanism and shock-tube test data under different conditions. The THU and CTH mechanisms also show similar soot concentration prediction. The global reaction of diesel fuel decomposed into n-heptane and toluene with mole fraction 7:3 was built to accelerate the decomposition and advance ignition timing. Kinetic constants of soot oxidation reactions were adjusted to reduce the soot oxidation rate. The THU mechanism was coupled with the KIVA-3V Release 2 code to model diesel combustion processes in the constant-volume combustion vessel and optical diesel engine of Sandia. The predicted ignition delay, in-cylinder pressure and heat release rate match the experimental results well. The predicted spatial and temporal soot concentration distributions have similar trend with the experiments.     

Sorption of lower alcohols in poly(ethylene terephthalate)

This paper presents equilibrium sorption and kinetics of lower alcohols in a 1.5 μ thick, biaxially oriented PET film. Methanol, ethanol, n-propanol and iso-propanol have been studied for the solubility and sorption kinetics in this film to understand how these properties change with penetrant size and branching. It is observed that n-propanol shows dual mode characteristics at all activities whereas the other three penetrants show Flory-Huggins uptake at high activities. Infinite dilution solubility is estimated and compared with that of esters, ketones and other hydrocarbons previously reported. The dispersive solubility parameter, δ_d is found to correlate well with the solubility of penetrants with the same functional group. The hydrogen bonding parameter, δ_h is observed to influence the solubility of penetrants with the same carbon number but different functional groups. This correlation with the solubility parameters may be extended to other functional groups and used to predict the infinite dilution solubility of larger penetrants in PET. Diffusion coefficients in the Fickian kinetics regime and Berens-Hopfenberg parameters in the non-Fickian kinetics regime have been evaluated. Diffusivity increases with concentration and decreases with size. Diffusion coefficient of iso-propanol is an order of magnitude lower than that of n-propanol due to branching effects.     

The liquid—liquid equilibrium for activity coefficient determination

A method based on liquid—liquid equilibrium is proposed for the determination of activity coefficients. The reliability of this procedure is tested on the systems cyclohexane—benzene, cyclohexane—toluene, n-hexane—benzene, n-heptane—toluene.     

Sorption kinetics and equilibria in annealed glassy polyblends

The sorption kinetics and equilibria of n-hexane in glassy polyblends of polystyrene and poly(2,6 dimethyl-1,4 phenylene oxide) were studied as a function of annealing conditions. Cast film samples were annealed 20°C above their respective glass transition temperatures for two hours and twenty-four hours. The rate of relaxation-controlled (Case II) sorption of n-hexane in these films was reduced markedly consequent to annealing. The effect of annealing on the sorption kinetics and the independently determined film densities was more pronounced for the poly(phenylene oxide)-rich samples. Although sorption rates were reduced by as much as a factor of 100, the sorption equilibrium was insignificantly affected by annealing. Super Case II transport was observed for the slow absorbing annealed samples whereas the more rapid sorption in the unannealed samples followed ideal Case II kinetics. The more pronounced effects of annealing for the poly(phenylene oxide)-rich samples on sorption rates and film densities were explained by considering the increasing difference between the film T_g and the drying temperature used in the original film preparation for the poly(phenylene oxide)-rich samples. These results suggest that glassy polymers, cast and dried well below their glass transition temperatures, will be subject to large long-term reductions in absorption rates and specific volume. Moreover, residual, excess free volume significantly affects relaxation-controlled absorption of vapors in partially annealed glassy polymers.     

The effect of humidity on water sorption in photoresist polymer thin films

A quartz crystal microbalance technique has been utilized to measure water sorption and desorption in three photoresist polymers: poly(p-hydroxystyrene), novolac, and bis-triflouromethyl carbinol substituted poly(norbornene). The humidity of the sample environment was varied to determine the rate and amount of water absorbed into the photoresist thin films as a function of local environmental conditions. At 100% absolute humidity, the polymers were found to absorb 9.8, 2-3, and 5-8 wt%, respectively. The sorption and diffusion of water into the polymer thin films was observed to initially follow Fickian behavior in the low fractional mass uptake regions (M_t/M_∞<0.6), but concentration dependent diffusion behavior was seen at higher levels of water uptake. All films sorbed and desorbed water rapidly with the majority of the water uptake or loss occurring in the first few seconds of exposure.