A detailed study of the viscoelastic nature of vapor sorption and transport in a cellulosic polymer. I. Origin and physical implications of deviations from Fickian sorption kinetics

Various aspects of the kinetics of sorption of acetone vapor by cellulose acetate films at 30°C have been studied in detail, the principal aim being to understand more thoroughly the physical nature and causes of non-Fickian behavior in this and other similar polymer-micromolecular penetrant systems. Particular attention was given to the changes in sorption (including absorption, desorption, and resorption) kinetics caused by (a) systematic variation of the vapor pressure of acetone in different ways and (b) changes in membrane thickness. It has been shown that both viscous volume swelling relaxation and longitudinal differential swelling stress effects must be invoked, in order to explain fully the observed behavior. Detailed analysis of two-stage sorption kinetics indicated (1) reasonable agreement between estimates of the diffusion coefficient reported by different authors, as long as a consistent analysis of the first stage is used, although the significance of the values given is open to some doubt, because the said first stage is found not to be free of non-Fickian features; and (2) reasonable conformity of the second stage to a first-order volume relaxation process (except a long times), with a relaxation frequency strongly dependent on the width of the concentration interval covered by the sorption experiment (and hence on the applied “osmotic stress”). The close similarity of second-stage sorption to nonlinear viscoelastic creep behavior, previously found in the cellulose-water system was confirmed and is taken further here, by demonstrating semiquantitative agreement between the corresponding “elastic swelling” and mechanical bulk moduli. ©1995 John Wiley & Sons, Inc.     

A detailed study of sorption equilibria and kinetics of a model disperse dye in cellulose acetate

A detailed investigation of the sorption of 4-aminoazobenzene by cellulose acetate films from aqueous solution is reported. Sorption isotherms at 75 and 60°C were linear up to saturation, in agreement with previous findings that have led to the conclusion that cellulose acetate-disperse dye systems are thermodynamically ideal. Thermodynamic analysis of these data also gave results consistent with such previous findings. The isotherms for 45 and 25°C, on the other hand, exhibited increasing curvature, in line with similar recent findings for a variety of hydrophobic polymer-disperse dye systems, and consistent with the presence of some strong absorption sites. However, the situation appears to be more complex than envisaged by simple dual-mode sorption theory. Early time desorption kinetic data were found to be consistent with Fick's law, with no indication of any significant dependence of the diffusion coefficient D on concentration (in the medium- to high-concentration range) or on film thickness. On the other hand, D was affected significantly by the history of film formation, the method of introducing the dye or heat treatment of the film. The origin of these effects was traced by DSC to definite microstructural differences. Late time kinetic data deviated significantly from the theoretical predictions based on the corresponding early time data, indicating a progressive slowdown of the desorption process. The deviations in question were generally more marked at higher temperature or film thickness, or when dyeing had been effected from the vapor phase, and were attributed to slow release of strongly adsorbed dye molecules. © 1994 John Wiley & Sons, Inc.     

Cellulose Nano Whiskers (CNWs) Loaded-Poly(sodium acrylate) Hydrogels. Part-I. Effect of Low Concentration of CNWs on Water Uptake

In this work, de-watered cellulose pulp(DCP), obtained from a paper mill, have been acid-hydrolyzed to yield cellulose nano-whiskers (CNWs). As revealed from FESEM measurements, these CNW were found to possess a median length of 258.5 nm, diameter of 35.2 nm, and an aspect ratio of 7.3. The CNWs were also characterized by TGA, XRD and FTIR analysis. The CNWs were found to possess a fairly high Crystallinity Index (CI) of 0.925. The addition of cellulose at low concentration range, i.e., from 25 to 125 mg (nearly 1.25 to 6.25 weight percent of polymer sodium acrylate) caused an enhancement in water uptake of resulting hydrogels .The CNWs-loaded poly(SA) hydrogels showed chain relaxation controlled swelling in the medium of pH 7.4 as was confirmed from the swelling exponent ‘n’ values obtained using power function law‥ The second order kinetic model was found to fit well to the kinetic water uptake data. However, all the samples, when prepared in the form of films, did not show any remarkable increase in their mechanical strength.     

Synthesis and thermal degradation kinetics of cellulose esters

Polymers that are biodegradable currently achieve high interest in material science since they offer reductions of landfill space during waste management as well as new end-user benefits in various fields of applications. In this work, cellulose esters such as cellulose benzoate, cellulose succinate and cellulose cinnamate were prepared using dimethylaminopyridine along with dimethylaminopyridine-p-toluene sulfonic acid catalyst. Films of cellulose esters were cast from solution. Cellulose esters were characterized by spectral methods such as infrared, nuclear magnetic resonance, thermal method such as thermogravimetric analysis. Various methods of kinetic analysis were compared in the case of thermal degradation of the cellulose and cellulose esters. Copyright­© 2003 John Wiley & Sons, Ltd.     

Optical vs. direct sorption and swelling measurements for the study of stiff-chain polymer-penetrant interactions

This work involves interferometric ‘optical thickness’ and refractive index measurements performed in an optical thickness meter (OTM), on supported cellulose acetate (CA) films equilibrated with various activities of methylene chloride (MC) vapor. The relevant equilibrium sorption and volume swelling isotherms were determined by application of the Claussius-Mossotti equation on the assumption that these films swell unidimensionally along the thickness direction, and were compared with corresponding direct equilibrium sorption (weight gain), elongation and thickness dilation measurements on similar free films performed in a vacuum sorption/swelling apparatus (VSA) and complemented with refractive index data. Combined elongation and thickness dilation data from the VSA showed that free glass-cast CA films exhibit pronounced swelling anisotropy. The said anisotropy, although it cannot be completely eliminated, by conditioning at high degrees of swelling, does not appear to affect the extent of volume swelling significantly, thus permitting quantitative comparison of sorption and swelling isotherms determined by the VSA and the OTM. Such comparison showed satisfactory agreement between these two sets of results up to an MC uptake of ca. 0.4 gMC/cm³ of dry CA corresponding to a degree of swelling of ca. 0.2. Increasing discrepancies are observed at higher MC concentrations, which are attributable to breakdown of the assumption used that the supported films swell unidimensionally along the thickness direction. The present CA-MC volume swelling data exhibit the negative deviation from volume additivity on mixing typical glassy polymers.     

Mass and momentum transfer in polymers. III. Effects of liquid penetrants on tensile stress relaxation of amorphous polymers

Sorption, diffusion, swelling, and tensile stress relaxation measurements were made at room temperature (23°C) for the systems poly(n-butyl methacrylate) (PBMA) with liquid methanol and ethanol, and poly(methyl acrylate) (PMA) with liquid water. Stress relaxation curves for the fully swollen polymers could be superimposed approximately with those for the dry polymers by appropriate shifting along the long axes. For PMA–water the measured curve for stress relaxation with concurrent sorption could be predicted accurately by using a moving boundary theory with data measurements of stress relaxation of the unswollen and swollen polymer combined with sorption data. The modified moving boundary theory is generalized to include the effects of dimension changes through swelling and the larger effects of plasticization associated with sorption of liquids. This improved theory accurately predicts measured curves of stress relaxation with concurrent sorption for the PBMA–alcohol systems from individual stress relaxation, sorption, diffusion and swelling data. The general approach should be applicable to other amorphous polymer–liquid swelling agent systems. The anisotropic nature of swelling of polymer films and its effect on calculated diffusion coefficients are discussed briefly.     

An inverse gas-chromatographic study of the interaction of water with some cellulose derivatives

The sorption isotherms for water on cellulose triacetate, cellulose acetate (degree of substitution 2.45), cellulose monoacetate (degree of substitution 0.89), and ethyl cellulose were measured by finite-concentration inverse gas chromatography. The isotherms for cellulose monoacetate were also measured with a vacuum microbalance. Polymer–solvent interaction parameters and partial molar heats of sorption at zero concentration of water were estimated from the extrapolated data, but kinetic effects and isotherm curvature lowered the precision of these results. The water sorption isotherms were examined according to the Zimm cluster theory, and the results were compared to those for cellulose and (hydroxypropyl)cellulose.     

Determination of standard isotherms of the sorption of some vapors with cellulose

Standard isotherms of the sorption of water, methanol, and benzene vapors on cellulose using a cellulose standard are determined. The standard, namely, mesoporous cellulose with specific surface of up to 350 m2/g, is obtained by the method of exchanging water in swollen cellulose with organic solvents. A comparison of the experimental sorption isotherm with the standard isotherm makes it possible to determine the specific surface of celluloses accessible a the given sorbate and, in combination with the Brunauer-Emmett-Teller adsorption equation, to characterize their surface properties. The identity of the sorption properties of the initial and dewatered (porous) celluloses relative to active vapors is shown, which evidences the assumed mechanism of swelling as the sorbent's division into morphological structures with the formation of new surface. A comparative analysis of the sorption properties of cellulose and silica, whose nature of active sorption centers is similar (weak acid hydroxyl groups), has been made. The affinity of the standard isotherms and close values of the cross-sectional area of different sorbates on both sorbents testify the similarity in their sorption behavior. Thus, the processes of sorption with rigid and swelling sorbents can be regarded in a unified context. Therefore, the adsorption models developed for rigid sorbents can be applied to cellulose sorbents to analyze their sorption properties.     

Physically insightful modeling of non-Fickian kinetic regimes encountered in fundamental studies of isothermal sorption of swelling agents in polymeric media

The kinetics of sorption of micromolecular swelling agents by polymeric media often deviates from normal Fickian behavior in various ways, which have to be understood and interpreted, with the aid of appropriate models, in terms of the underlying physics. One difficulty which arises in this respect is that salient aspects of the observed kinetic behavior can be mimicked by extraneous effects, in the form of significant deviation from a boundary condition or of imperfect macroscopic homogeneity of the polymer film (modeled in both cases as a surface resistance to penetrant transport). Such effects have, in fact, been invoked (notably by Hansen (2010) [11]) to question the significance of conclusions drawn from modeling approaches based on the effect of intrinsic bulk polymer properties, leading to delayed (viscous) swelling and to build-up and decay of differential swelling stresses. We present here a brief critical account (following the mainstream modeling line initiated by Crank) of typical results concerning various salient aspects of observed non-Fickian sorption kinetics and of the comparative possibility of achieving satisfactory general interpretation thereof, in terms of approaches based on the aforementioned extraneous, versus intrinsic bulk property, effects. We find that the latter approach has been successful so far, both computationally and physically, by establishing a close physically significant analogy between non-Fickian sorption, and (both linear and non-linear) viscoelastic mechanical deformation, behavior. The former approach, on the other hand, proves weak on both counts.     

THE EFFECT OF CHAIN LENGTH OF POLYETHYLENE GLYCOL ON PROPERTIES OF CASTOR OIL BASED POLYURETHANE ELASTOMERS

ABSTRACT

Polyurethane (PU) elastomers from castor oil based polyol, polyethylene glycol (PEG) of various molecular weight (200, 400, and 600) and toluene diisocyanate were prepared in the form of transparent sheets. The sorption, mechanical and thermal properties have been studied. The solubility parameter, molecular weight between two crosslinks and degree of crosslinking of PU samples were calculated from equilibrium swelling experiments. The kinetic study of swelling revealed that sorption is anomalous in nature in all the samples. Diffusion coefficient (D) and sorption coefficient (S) were found to decrease with an increase in chain length of PEG. The stress-strain data showed that the elastomers obtained using PEG-200 gave the best mechanical properties. The thermal degradation of all elastomers starts at ～250°C, regardless of the PEG chain length. The values of activation energy of degradation were in the range of 60–72 kJ/mole.     

Grafting of arginine and glutamic acid onto cellulose for enhanced uranyl sorption

The grafting of arginine and glutamic acid on cellulose (through an intermediary step of chlorination) allows improving uranyl sorption of the biopolymer. The sorbents (Arg-Cell and Glu-Cell) were characterized by elemental analysis, FTIR spectrometry, XRD, SEM-EDX analysis and TGA. The sorption efficiency increases with pH; this can be attributed to the deprotonation of carboxylic acid and amine groups and to the formation of polynuclear hydrolyzed uranyl species. Sorption isotherms (fitted by the Langmuir equation) show sorption capacities at saturation of the monolayer of 147 and 168 mg U g^?1 for Arg-Cell and Glu-Cell, respectively (compared to 78 mg U g^?1 for raw cellulose); maximum sorption capacities at equilibrium (experimental values) reach 138, 160 and 73.4 for Arg-Cell, Glu-Cell and cellulose, respectively. Uranyl sorption is endothermic and is spontaneous for amino acid derivatives of cellulose (contrary to exothermic for cellulose). Uptake kinetics for the different sorbents are fitted by the pseudo-second-order rate equation. Uranium can be desorbed using sulfuric acid solutions, and the sorbents can be recycled for a minimum of five cycles of sorption/desorption: the decrease in sorption capacities at the fifth cycle does not exceed 13%.     

The Structure of Cellulose by Conformational Analysis. Part 5. The Cellulose Ii Water Sorption IsothermXS

Exact values of the sorption energies of single molecules of water on all available sorption sites of crystalline cellulose II have been obtained by conformational analysis. The sorption energies are equated to the total energy (E_tot ) of interaction between the water molecule and all the suitable atomic groups of the cellulose. E_tot is composed of van der Waals, H-bond, and electrostatic energies. The interferences of water molecules on vicinal sorption sites were obtained. Sites in which such interference can occur were identified for crystalline cellulose II. Sorption energy in crystalline cellulose II appears to depend only on the interaction of water with surface sorption sites of the crystal. There appears to be favorable sorption on 1) sites exerting high attractive forces, and 2) sites which are exposed and protrude from the crystal surface. Sites recessed from the crystal surface are generally repulsive due to strong interactions with neighboring groups. All the sorption energies of the “monolayer” were calculated. Very strong sorption sites cannot always form a second layer because of strong steric hindrance from vicinal groups. Sorption capacities of crystalline cellulose II were calculated, and the isotherm of the schematic five chain crystallite used was constructed by theoretical means. The results obtained were briefly compared with those for cellulose I crystallites and amorphous cellulose. The inflection points of the isotherm and the variability of Dent's k ₁ constant for the water monolayer with relative humidity for the cellulose I and II isotherms were also calculated by theoretical means.     

Water uptake and dye sorption studies of chemically crosslinked highly swollen novel ternary acrylamide‐based hydrogels including citraconic acid and sodium acrylate

Highly swollen hydrogels made by the polymerization of acrylamide (AAm) with some anionic monomers such as citraconic acid (CITA) and sodium acrylate (SA) were investigated as a function of composition to find materials with swelling and dye sorption properties. Highly swollen AAm/CITA/SA or AAm/SA/CITA hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with CITA and SA as co‐monomers and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4‐butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. Chemically crosslinked AAm/CITA/SA or AAm/SA/CITA hydrogels were used in experiments on sorption of water‐soluble monovalent cationic dye such as “Nil blue” (Basic Blue 12; BB 12). Equilibrium percentage swelling values of AAm/CITA/SA or AAm/SA/CITA hydrogels were calculated in the range of 1797–22,098%. Some swelling kinetic parameters were found. Diffusion behavior of water was investigated. Water diffusion into the hydrogels was found to be non‐Fickian in character. For sorption of cationic dye, BB 12 into the hydrogels was studied by batch sorption technique at 25°C. AAm/CITA/SA or AAm/SA/CITA hydrogels in the dye solutions showed coloration, whereas AAm hydrogel did not show sorption of any dye from the solution. The sorption capacity of AAm/CITA/SA or AAm/SA/CITA hydrogels was investigated. At the end of the experiments, 21.70–78.91% BB 12 adsorptions were determined. Copyright © 2007 John Wiley & Sons, Ltd.     

Nonlinear modeling of equilibrium sorption of selected anionic adsorbates from aqueous solutions on cellulosic substrates. Part 1: model development

A new nonlinear isothermal sorption model, incorporating Donnan equilibrium and electrical neutrality in the classical sorption model of direct dyes onto cellulosic substrates, as model adsorbates, is proposed. The nonlinear isothermal model was used to simulate equilibrium sorption of adsorbates containing ionic charges (z) of −2 to −4 on cellulose adsorbents at various temperature (T) and sodium chloride concentrations ([NaCl]). A detailed analysis of simulation results demonstrates that results based on the nonlinear sorption model highly agree with those based on the log-linear sorption model when the deviation in the concentration of sodium ions in the aqueous solution ([Na⁺] _S ) relative to [NaCl] used in the sorption system is restricted to <5.0%. Compared to the log-linear model, the nonlinear model avoids using graphical techniques that are relatively insensitive for determining important sorption parameters such as the internal accessible volume (V) and the standard affinity associated with sorption (−Δμ°). The nonlinear sorption model was used to examine the correlation of fit for previously reported sorption data. The model parameters V and −Δμ° based on curve fits were used to estimate V for cellulose as well as −Δμ°. The values were found to match those based on the conventional log-linear model when deviations of [Na⁺] _S relative to [`([\textNa ⁺ ]_S )] \overline{{[{\text{Na}}^{ + } ]_{S} }} were below 5%. The nonlinear model therefore provides a convenient and accurate technique to interpret the sorption of a range of anionic adsorbates on cellulosic substrates.     

Swelling and sorption in polymer–CO2 mixtures at elevated pressures

Experimental data on gas sorption and polymer swelling in glassy polymer—gas systems at elevated pressures are presented for CO₂ with polycarbonate, poly(methyl methacrylate), and polystyrene over a range of temperatures from 33 to 65°C and pressures up to 100 atm. The swelling and sorption behavior were found to depend on the occurrence of a glass transition for the polymer induced by the sorption of CO₂. Two distinct types of swelling and sorption isotherms were measured. One isotherm is characterized by swelling and sorption that reach limiting values at elevated pressures. The other isotherm is characterized by swelling and sorption that continue to increase with pressure and a pressure effect on swelling that is somewhat greater than the effect of pressure on sorption. Glass transition pressures estimated from the experimental results for polystyrene with CO₂ are used to obtain the relationship between CO₂ solubility and the glass transition temperature for the polymer. This relationship is in very good agreement with a theoretical corresponding-states correlation for glass transition temperatures of polystyrene-liquid diluent mixtures.     

The influence of transverse differential swelling stresses on the kinetics of sorption of penetrants by polymer membranes

The influence of transverse differential swelling stresses on the kinetics of sorption of a penetrant in a polymer membrane exhibiting linear viscoelasticity is described by a model developed from the much simpler one of Crank. Sorption and transverse swelling kinetic curves are computed numerically. The character of absorption and desorption curves is examined systematically mainly as a function of (i) the magnitude of the stresses set up and of the stress-dependence of the diffusion coefficient, (ii) the relative rates of stress relaxation and of diffusion, and (iii) the degree of plasticization or “softening” of the polymer by the penetrant. It is shown that important general features of experimental sorption kinetic curves can be reproduced satisfactorily under well defined conditions. Attention is also given to transverse swelling kinetic curves. Their correlation with the corresponding sorption curves is examined briefly but systematically and discussed with reference to experimental data.     

Simultaneous in situ measurement of sorption and swelling of polymers in gases and supercritical fluids

In this work, a novel method to simultaneously measure in situ swelling and sorption of gases and supercritical fluids in polymers in a commercially available apparatus is proposed. A gravimetric approach reported recently is applied to measure sorption whereas swelling is determined in situ by direct visualization. The proposed method has been used to study the sorption and swelling of carbon dioxide in poly (methyl methacrylate) and the obtained results are compared to previously published literature data. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Effect of temperature on high pressure cellulose compression

The effect of temperature during cellulose compression has been studied using mechanical testing, particle size analysis, density and pressure–volume–temperature (PVT) measurements, crystallinity index, scanning electron microscope photographs and water sorption isotherms. Commercial cellulose powder samples with different crystallinity levels were compacted at high pressure (177 MPa) for 10 min at two different temperatures: 25 and 160 °C. Three point bending test results for compressed samples are discussed. When pressure was applied directly to powders at room temperature, the cellulose sample with the highest level of crystallinity showed an increase in its crystallinity index of about 5 %, while this was about 22 % for the sample with the lowest level. These increases were even higher at 160 °C attaining 8 and 33 % respectively. Using density measurements, a densification phase related to this crystallinization was observed, and the PVT diagrams from different cellulose samples showed that this was associated with high temperatures. Water sorption isotherms were made on cellulose samples before and after compression. They showed a diminution of cellulose sorption capacity after compression at 160 °C, revealing the effect of temperature on high-pressure cellulose compression, reducing specific surface area. Events of this nature suggest a sintering mechanism, when temperature is associated with high pressure during cellulose compression.     

Sorption and diffusion of aliphatic hydrocarbons into crosslinked natural rubber

The sorption and transport of four aliphatic hydrocarbons into natural rubber crosslinked by different vulcanization systems [conventional (CV), efficient (EV), peroxide (DCP) and a mixed system consisting of sulfur and peroxide (mixed)] were investigated in the temperature interval of 28–60°C. Of the four systems, natural rubber vulcanized by DCP exhibited lowest penetrant uptake. It was observed that the kinetics of liquid sorption in every case deviates from the regular Fickian trend, characteristic of sorption of liquids by rubbers. The diffusion coefficient, activation energy of sorption, enthalpy, entropy, and the rubber-solvent interaction parameter were evaluated for the four systems from the swelling data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 725–734, 1997     

Swelling and dissolution of cellulose, Part V: cellulose derivatives fibres in aqueous systems and ionic liquids

The swelling and dissolution mechanisms of several cellulose derivatives (nitrocellulose, cyanoethylcellulose and xanthate fibres) are studied in aqueous systems (N-methylmorpholine-N-oxide—water with various contents of water, hydroxide sodium—water) and in ionic liquids. The results are compared with the five modes describing the swelling and dissolution mechanisms of cotton and wood cellulose fibres. The mechanisms observed for the cellulose derivatives are similar to the ones of cotton and wood fibres. Swelling by ballooning is also seen with cellulose derivatives, showing that this phenomenon is linked to the fibre morphology, which can be kept after undergoing a heterogeneous derivatisation. Patrick Navard and Thomas Heinze—Members of the European Polysaccharide Network of Excellence (EPNOE),