Reverse osmosis characteristics of cellulose acetate butyrate membranes

Cellulose acetate butyrate membranes were cast from five different formulations. The pure water flux through the membrane increased with evaporation period. The separation of 4000 ppm NaCl aqueous solution remained unchanged until it reached a critical flux; at that point, separation decreased inversely proportional to the flux. Scanning electron microscope photography of the membranes corresponding to each evaporation period is reported.     

Permeation of water and sodium chloride through cellulose acetate

The factors contributing to the selective permeation of water and sodium chloride through cellulose acetate membranes have been examined by the use of radioactive tracers. With decreasing acetyl content both the partition coefficient (solubility) and diffusion coefficient of water increased, the latter the more sharply. The effect was even more pronounced for salt, indicating that increasing selectivity with acetyl content stems mainly from increasingly preferential restrictions on salt mobility. Trends identical with those mentioned for decreasing acetyl content were found for increasing amounts of cellulose acetate solvents that had been extracted with water to yield more highly swollen membranes. A free-volume treatment for diffusion of small molecules below the glass transition temperature with the aid of subgroup motion in the polymer is used for both components. The water content of the membrane at (or near) saturation emerged as the predominant factor in the permeation behavior. In view of the similarity in the activation energies of water and salt diffusion the far steeper dependence of the salt diffusion coefficient on water content could not be accounted for by size differences between the diffusing species and has been attributed to confinement of salt ions to locations at which multiple water contacts are feasible.     

Permeation of sodium dodecyl sulfate through polyaniline-modified cellulose acetate membranes

The preparation of polyaniline (PANi)-cellulose acetate (CA) blends by casting films from a suspension, is reported. Two membranes were prepared from different solvents, one with a homogeneous and the other a heterogeneous dispersion of PANi in CA matrices. The membranes were characterized by X-ray diffraction, SEM, DSC, and FTIR, and the results were compared with those obtained for pure CA and PANi films. The transport properties of water and sodium dodecyl sulfate (SDS) in membranes of the PANi-CA blends and of CA were analysed. The transport of SDS and water depends on both the bulk/polymer density and the PANi content. In the homogeneous blend, the interaction between SDS and the polymer plays an important role in the transport mechanism. An irreversible interaction is observed, which can be monitored by UV-vis spectroscopy. The spectra of homogeneous, highly transparent PANi-CA blends show a pronounced sensitivity to SDS concentration, with detection limits [SDS]≥0.1 mM for films with a PANi concentration of 0.05% w/v.     

Reverse osmosis separation of binary organic mixtures using cellulose acetate butyrate and aromatic polyamide membranes

A systematic investigation has been conducted to demonstrate applicability of reverse osmosis (RO) fractionation of organic liquid mixtures by laboratory-prepared cellulose acetate butyrate (CAB) and aromatic polyamid (PA) membranes. The determination of preferential sorption was also conducted by using liquid chromatography technique. It was found that reverse osmosis was applicable to the fractionation of organic liquid mixtures. It was also found that the component of the binary mixture that is enriched in the membrane permeate can be predicted by considering the preferential sorption and Stokes' radius for each constituent of the feed mixtre.     

Physical aging and biaxial creep in cellulose acetate butyrate

Torsional and tension-torsion creep studies have been performed on cellulose acetate butyrate at 65°C. The aging shift factor, μ, at this temperature has been determined to be 0.85. This is somewhat higher than 0.75 which was suggested as a maximum value for cellulose acetate butyrate (5). Axial stresses cause the torsional retardation times to become shorter. The change in retardation time is mainly determined by the magnitude of the axial stress and not by the length of time during which the axial stress is applied. Torsional stresses cause the axial retardation times to shift in a similar manner. The shifting of retardation times follows a maximum shear stress criterion.     

The effect of chelation on the selective transport of alkaline-earth metal ions in asymmetric cellulose acetate hyperfiltration membranes

The rejection of calcium and/or magnesium ion by asymmetric cellulose acetate hyperfiltration membranes is increased significantly by formation of the corresponding alkaline-earth metal chelate. Typically solute fluxes are reduced by a factor of 5 consequent to chelation with ethylenediaminetetraacetic acid (EDTA) at pH 6.0. Selective chelation and, in turn, selective transport of magnesium is observed when equimolar solute mixtures corresponding to 1:1:1 magnesium:calcium:EDTA are hyperfiltered. Under these conditions, calcium successfully competes for the stoichiometrically limiting EDTA, and the rejection of magnesium is lower than the rejection observed for the hyperfiltration of the MgEDTA^2? complex in the absence of competitive calcium. Alternatively, the rejection of the CaEDTA^2? complex is increased under these identical conditions, presumably as a consequence of specific interactions between the available free magnesium and the cellulose acetate membrane. The effects reported here all seem to be related to reductions in solute diffusivity associated with the increased size of the alkaline-earth metal ion complex.     

Dispersion and properties of cellulose nanowhiskers and layered silicates in cellulose acetate butyrate nanocomposites

The aim of this work was to develop well dispersed nanocomposites, in a non water soluble polymer using a non aqueous, low polarity solvent as a dispersion medium. The nanoreinforcements were cellulose whiskers and layered silicates (LSs) and matrix was cellulose acetate butyrate (CAB). Before nanocomposite processing, a homogenizer was used in combination with sonification to achieve full dispersion of the nanoreinforcements in a medium of low polarity (ethanol). After processing, the cellulose nanowhiskers (CNW) showed flow birefringence in both ethanol and dissolved CAB, which indicated well dispersed whiskers. The microscopy studies indicated that the processing was successful for both nanocomposites. The CNW showed a homogeneous dispersion on nanoscale. The LS nanocomposite contained areas with lower degree of dispersion and separation of the LS sheets and formed mainly an intercalated structure. The produced materials were completely transparent, which indicated good dispersion. Transparency measurements also indicated that the nanocomposite containing CNW showed similar performance as the pure CAB. Dynamic mechanical thermal analysis (DMTA) showed improved storage modulus for a wide temperature range for both nanocomposites compared with the pure CAB matrix. This study indicated that CNW have a potential application in transparent nanocomposites based on fully renewable resources. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phenol transport in cellulose acetate membranes

Past detailed studies of solute transport through reverse-osmosis membranes have been conducted only with simple salts. The present work with phenol was undertaken largely because of the practical observation that the transport of low molecular weight organics is much more rapid than that of the salts. Studies of phenol sorption from dilute aqueous solution indicate that the diffusion coefficient for phenol in water-saturated 39.8 wt.-% acetyl cellulose acetate is 9.6 × 10^-10 cm.²/sec., and the equilibrium distribution coefficient between the acetate phase and water is 42. Thus, the diffusion coefficient is quite close to that measured for sodium chloride, and the higher permeability of the membranes to phenol can be attributed entirely to their greater sorption of this solute. In direct osmosis experiments performed with significant water flow a measurable interaction or positive coupling between water and phenol flows has been observed. Further evidence of flow coupling is derived from reverse osmosis experiments in which significant negative solute rejection is observed; i.e., the permeate is enriched in phenol by as much as 20%. It is shown that a solution-diffusion transport model is not adequate to rationalize the results, and a more complex transport model is apparently required.     

Ion movements in cellulose acetate membranes

The behavior of ions in a cellulose acetate membrane was discussed from the standpoint of mobilities obtained from the membrane potentials. The mobilities of univalent ions larger in radius or divalent ions relative to Na⁺ ion mobility in the membrane are much different from those in aqueous solutions. The order of the mobilities of ions in the membrane is shown quantitatively. The mobilities of the ions with radii larger than a certain value in the membrane decrease with increase in their size. This could be explained by the physical friction between the ion and the membrane wall. This friction is of importance as the ionic radius comes close to the intermolecular gaps between polymer chains. The mobilities of Na⁺ anyd 1^? ions in the membrane are (2–3) × 10^?7 cm²/sec-V and are about three to four orders of magnitude less than those in aqueous solutions.     

Performance characterization of cellulose acetate and poly(vinylpyrrolidone) blend membranes

Hydrophilic ultrafiltration membranes have been prepared by blending cellulose acetate (CA) as a matrix polymer with increasing concentrations of poly(vinylpyrrolidone) (PVP) using N,N′‐dimethylformamide as the solvent. It is observed that the presence of PVP beyond 50 wt % in the casting solution did not form membranes. Prepared membranes have been subjected to ultrafiltration characterizations such as compaction, pure water flux, water content, and membrane hydraulic resistance. The results indicate significant changes in the characteristics upon the addition of PVP, which may lead to improved performance. The porosity, pore size, and molecular weight cut‐off of the membranes also increase as the concentration of PVP increases. It is estimated that the pore radius of the CA/PVP membranes increases from 30 to 63 Å, when the concentration of PVP increased from 0 to 50 wt %. This is in agreement with the results obtained from scanning electron microscopic studies. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

A new perspective and comparative study on demixing and gelation behavior of cellulose acetate,cellulose acetate propionate and cellulose acetate butyrate ternary solutions

Cellulose acetate (CA), cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB) were fabricated as membrane via nonsolvent induced phase separation process. N,N‐Dimethylformamide (DMF) and N,N‐Dimethylacetamide (DMAc) as solvents and water as nonsolvent were employed. Ternary phase diagrams for all six ternary systems were constructed using Flory‐Huggins theory. In this way, cloud points as well as Berghman's points were determined. Modulus of polymers steepened in various concentration of solvent/nonsolvent mixtures were measured to find the weight fraction of polymer (w_p) in which vitrification takes place. W_P values for CA, CAP, and CAB were obtained 0.59, 0.67, and 0.74 in presence of DMF while those were 0.69, 0.74, and 0.84 in presence of DMAc; whereas glass transition temperatures (T_g) for three polymers were determined 180°C, 142°C, and 101°C correspondingly. Pure water flux for CA, CAP, and CAB membrane increased from 75.7 to 83.4 and 290.3 and from 109.6 to 116.1 and 400.3 L/m² h bar when DMF and DMAc were used as solvents, respectively. Results revealed that as T_g of polymer decreases, the membrane structure vitrifies at higher polymer concentration with more porous structure, bigger pores, higher permeate flux followed by decrease in mechanical strength. POLYM. ENG. SCI., 58:1135–1145, 2018. © 2017 Society of Plastics Engineers     

Formation of asymmetric cellulose acetate membranes

Cellulose acetate membranes were prepared from casting solutions containing dioxane as a solvent and varying concentrations (up to 6%) of maleic acid as an additive. Coagulation took place in water at different temperatures. The effect of these variables on membrane structure and membrane properties is related to two phenomena of phase separation in the system cellulose acetate/dioxane/water, viz. gelation in the toplayer and liquid-liquid phase separation in the sublayer of the membrane. We adopted a solution transport model which correlates membrane flux with the skin thickness and membrane salt rejection with the compactness (microstructure) in the skin. Effects of variables such as maleic acid concentration and coagulation temperature on the position of curves in the phase diagram and on membrane properties are discussed. It is concluded that more work should follow on the kinetics of the phase changes mentioned.     

Freezing and nonfreezing water in cellulose acetate membranes

The relative amounts of freezing and nonfreezing water in various cellulose acetate (CA) membranes were determined by differential scanning calorimetry. It was found that: (1) A significant fraction (17–40%) of the water (1.0–3.1 g H₂O per gram dry CA) in any membrane does not freeze at temperatures as low as ?60°C. (2) The amount of nonfreezing bound water (0.4–0.7 g nonfreezing water per gram dry CA) depends upon the nature of the membrane and is significantly higher than the total amount of water (all of which is nonfreezing) absorbed from liquid water by a dense film of the same polymer (～0.18 g water per gram dry CA). The structures of the membranes were studied by scanning electron microscopy. The results suggest that the amounts of nonfreezing water in cellulose acetate membranes decrease with the increase in the packing density (compactness) of the polymer within the membrane. In dense films, the extent of polymer–polymer interactions within the polymeric matrix is high, and therefore the macromolecular chains are less accessible to bind water.     

Morphological development of polypropylene in immiscible blends with cellulose acetate butyrate

Isotactic polypropylenes (iPP) with different melt flow indexes were melt blended with cellulose acetate butyrate (CAB) and then prepared into microspheres or nanofibers following a novel process of producing well dispersed CAB/iPP immiscible blends and subsequent removal of the CAB matrix. The morphologies of iPP microspheres were investigated by a scanning electron microscopy, and the dimensions of iPP microspheres were evaluated. The melt viscosities of iPP, CAB, and CAB/iPP blends were measured by using a capillary rheometer. The influences of the viscosity, viscosity ratio, and composition ratio of iPP/CAB on the morphology formation of iPP in CAB matrix were studied.     

The effect of chelation on the selective transport of alkaline earth metal ions in asymmetric cellulose acetate hyperfiltration membranes. II

The effects of chelation on the transport of calcium and magnesium, both separately and in a variety of admixtures, in a controlled series of asymmetric cellulose acetate membranes were characterized. Ethylenediaminetetraacetic acid (EDTA) and ethylenebis(oxyethylenenitrilo)tetraacetic acid (EGTA) were used as chelating agents for the alkaline earth metal ions. Asymmetric cellulose acetate membranes annealed at 70°, 75°, and 85°C were studied. Chelation of each of these alkaline earth metals ions in aqueous solutions at pH 6, by either EDTA or EGTA, significantly increased the overall hyperfiltration rejections of these metals by all the membranes studied. The increase in rejection varied montonically with the fraction of metal ion complexed. The higher rejection of metal chelates, compared to the rejection of unbound metal ions, was considered to be the result of the significantly larger size of the chelated species. Calculations suggested that selective (or competitive) chelation took place at pH 6 in a mixture of calcium and magnesium ions in the presence of a stoichiometrically limiting amount of chelating agent. Calcium successfully competed for most of the available chelating agent in equimolar aqueous solutions of chelating agent, calcium, and magnesium. The calcium rejection was explained primarily in terms of the effects of chelation per se on the effective size of the formed complex even in feeds comprised of these ternary solute mixtures. The complexation reaction between magnesium and EGTA is, however, so unfavorable at pH 6 that the Mg²⁺ ion remains uncomplexed even in the presence of an equivalent amount of EGTA. The observed increased rejection of magnesium ions, therefore, in ternary systems was explained by electroneutrality criteria and by solute–membrane interactions involving the various calcium species and the membranes.     

Movements of univalent ions in cellulose acetate membranes

Membrane potentials across the asymmetric membranes of cellulose acetate with various salt rejection properties have been measured for univalent ions. The behavior of ions in the membranes is discussed from the viewpoint of relative ionic mobilities calculated from the membrane potentials. The relationship between ionic mobilities and ionic radii in the membranes having salt rejections lower than 80% is almost the same as that in aqueous solutions. This implies that the ions in these membranes behave as if they exist in bulk water. However, the ionic mobilities in the membranes having salt rejections higher than 86% differ significantly depending on the ionic radii. It seems probable that the bound water influences the ionic mobilities in these membranes.     

The states of water in cellulose acetate membranes

Differential scanning calorimetric melting endotherms of wet and half-dried cellulose acetate membranes and salt distribution coefficients were studied to clarify the states of water in membranes. We have suggested that (a) there are four states of water in cellulose acetate membranes; (b) these states of water are those of completely free water, free water very weakly interacting with polymer, bound water which can contain salts, and bound water which rejects salts; (c) the semipermeability of membranes depends on the ratio of four states of water in membranes.     

Performance evaluation and antifouling analyses of cellulose acetate/nanodiamond nanocomposite membranes in water treatment

In this study, nanocomposite membranes based on cellulose acetate (CA) and nanodiamond (ND) were prepared by applying phase inversion methods. In order to achieve efficient dispersion and more hydrophilic NDs, they were functionalized via heat treatment (ND‐COOH). The prepared nanocomposite membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), contact angle, porosity measurement, tensile strength, and abrasion resistance techniques. Furthermore, the governing fouling mechanisms were determined by using classic models as well as combined fouling models. Moreover, the effect of precoagulation with polyaluminum chloride (PAC) on the humic acid (HA) filtration was investigated. The obtained results showed that in the presence of ND‐COOH, the abrasion resistance of nanocomposite CA membrane was three times higher than that of pristine CA membrane. Besides, the nanocomposite membranes with 0.5 wt % of raw and functionalized ND exhibited excellent hydrophilicity and PWF. The analysis of fouling mechanism based on Hermia's model revealed that the cake formation is prevailing mechanism for CA and CA/ND (0.5 wt %) membranes while for CA/ND‐COOH (0.5 wt %) membrane, experimental results are fitted by combined cake filtration‐complete blocking (CFCB) model. It confirms that pretreatment with PAC can significantly mitigate fouling and improve HA removal. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44873.     

Permeabilities of coagulated cellulose acetate dialysis membranes

The diffusive flux of NaCl and the hydraulic flux of pure water through coagulated cellulose acetate membranes are examined. Coagulated cellulose acetate membranes (without densification by heat treatment or drying) possess higher permeability than what may be expected from the permeabilities of the dry polymer. Their overall hydraulic permeability (ultrafiltration rate of water) is greatly dependent upon the membrane casting conditions and the resulting asymmetry of the membrane. On the other hand, the asymmetry of a membrane does not play as great a role in the diffusive permeability of a solute. With homogeneous membranes, higher diffusive flux is always accompanied by higher hydraulic permeability. With asymmetric membranes, this is not always true. The diffusive permeability of NaCl and the hydraulic permeability of water through coagulated cellulose acetate membranes can be controlled nearly independently. Consequently, high diffusive (NaCl) permeability with low hydraulic water permeability and vice versa can be obtained by varying the casting conditions and also by partially saponifying the denser portion of the membrane.