Structure and properties of composites of polyethylene or maleated polyethylene and cellulose or cellulose esters

Composites of linear low‐density poly(ethylene‐co‐butene) (PE) or maleated linear low‐density poly (ethylene‐co‐butene) (M‐PE) and cellulose (CEL), cellulose acetate (CA), cellulose acetate propionate (CAP), or cellulose acetate butyrate (CAB) were prepared in an internal laboratory mixer with 20 wt % polysaccharide. The structure and properties of the composites were studied with tensile testing, dynamic mechanical thermal analysis, differential scanning calorimetry, extraction with a selective solvent, Raman spectroscopy, and X‐ray diffraction. Composites prepared with M‐PE presented yield stress and elongation values higher than those of composites prepared with PE, showing the compatibilizer effect of maleic anhydride. Dynamic mechanical thermal analysis performed for M‐PE–CEL, M‐PE–CA, M‐PE–CAP, and M‐PE–CAB composites showed one glass‐transition temperature (T_g) close to that observed for pure M‐PE, and for M‐PE–CAP, another T_g lower than that measured for the polysaccharide was observed, indicating partial mutual solubility. These findings were confirmed by the extraction of one phase with a selective solvent, gravimetry, and Raman spectroscopy. X‐ray diffraction showed that the addition of CEL, CA, CAP, or CAB had no influence on the lattice constants of PE or M‐PE, but the introduction of the reinforcing material increased the amorphous region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:402–411, 2007     

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.     

An approach to the development of cellulose acetate ultrafiltration membranes

The film-casting solution consisted of a mixture of cellulose acetate, acetone, and aqueous magnesium perchlorate [Mg(ClO₄)₂:H₂O = 1:8.5], designated as polymer P, solvent S, and nonsolvent N, respectively. Using the composition P:S:N = 17: 69.2: 13.8 as reference, films were obtained from 19 different casting solutions in which the weight ratios S/P, N/S, and N/P were varied in different directions. The casting solution temperature was 0°C, and solvent evaporation period during film formation was minimum in most cases. The effects of variations of casting solution temperature and solvent evaporation period were also briefly studied. Reverse osmosis experiments with resulting membranes were carried out at 100 psig using 200 ppm NaCl–H₂O as the feed solution. Decrease in S/P, increase in N/S, and increase in N/P in the casting solution, decrease in temperature of the casting solution, and increase in solvent evaporation period tend to increase the size of pores on the surface of resulting membranes in the ascast condition. Increase in S/P in the casting solution, and increase in the temperature of the casting solution tend to increase the effective number of pores on the membrane surface. These results offer definitive physicochemical criteria in terms on solution structure–evaporation rate concept for developing useful cellulose acetate ultrafiltration membranes.     

Isothermal phase diagrams and phase‐inversion behavior of poly(vinylidene fluoride)/solvents/additives/water systems

Isothermal ternary phase diagrams of poly(vinylidene fluoride) (PVDF)/solvents/nonsolvent systems were produced using four different solvents, N,N‐dimethylacetamide (DMAc), 1‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and triethyl phosphate (TEP), and using water as a nonsolvent. The effects of the additives polyvinylpyrrolidone (PVP, M_w = 10,000), ethanol, and lithium perchlorate (LiClO₄) on the phase‐inversion behavior of PVDF/DMAc/water ternary system were investigated, with additive concentrations of 2 and 6 wt %, at temperatures of 25 and 70°C, respectively. Ethanol, glycerol, and water were used to study the cloud points of 10, 15, and 20 wt % PVDF/DMAc concentrations, at solution temperatures ranging from 30 to 70°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2150–2155, 2003     

Influence of the solvent and nonsolvent composition on the electrospinning of a cellulose acetate ternary system

A series of cellulose acetate (CA) ternary system solutions consisting of the CA, N,N‐dimethylacetamide, and various nonsolvents, such as 1‐propanol, 1‐hexanol, 1‐octanol, 1‐decanol, 1,3‐propane diol, and glycerol, were prepared, and the effects of the component composition on the solutions characteristics and electrospinning were examined. In particular, the effects of the nonsolvent concentration, structure, and degree of miscibility with other components were studied. In some cases, increasing the nonsolvent content increased the solution viscosity and facilitated the electrospinning process. However, we found that electrospinning was also governed by the structure of the nonsolvents and by the solution viscosity. An increase in the number of hydroxyl groups or an increase in the hydrocarbon chain length of the monohydroxyl alcohol nonsolvent improved the fiber formation. The calculated Hansen sphere [D_(S‐p)] values of the CA ternary system solution were then used to explain their electrospinnability. The increases in the hydrophilicity and hydrophobicity of system caused by changes in the nonsolvent structure increased the D_(S‐p) values and improved fiber formation in electrospinning process. The calculated D_(S‐p) values were also shown to be in good agreement with the obtained microscopy images of the electrospun fiber. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42819.     

Surface activity of aqueous solutions of cellulose acetate with low degree of substitution

Surface activity of aqueous solutions of cellulose acetate (CA) with total degree of substitution (〈F〉) ranging from 0.58 to 0.80 was examined. Critical micelle concentration (CMC) of the aqueous CA solutions, determined from the polymer concentration dependence of surface tension (γ), is unequivocally determined by 〈F〉, and an increase in 〈F〉 of CA brings about a lowering of the CMC. From light scattering measurements on aqueous solutions of CA with 〈F〉 = 0.8 at 20°C, it was revealed that in the vicinity of the CMC the micelles in the solution consist of c. four CA molecules, which is very close to the value obtained by analysing the data obtained from the mass action model. The surface tension of aqueous solutions of CA (〈F〉 = 0.8) in the polymer concentration range above the CMC was c. 0.74 times that of pure water over the temperature range 0–80°C.     

Preparation of Rh-containing cellulose acetate films and the chemistry of Rh in cellulose acetate

RhCl [P(C₆H₅)₃]₃ complexes have been incorporated in cellulose acetate as a dispersion medium using cosolvent (tetrahydrofuran). The interactions between Rh (I) complexes and cellulose acetate (CA) are examined by infrared spectroscopy and thermal analysis. The chemical reactivities of Rh–CA films have been investigated by reacting Rh sites with CO, H₂, O₂, and C₂H₄ in the temperature range 90–150°C and at a pressure of less than 1 atm. Three different Rh-carbonyls and a Rh-hydride species formed in CA are characterized by their infrared spectra. Treatment of 10 or 20 wt % Rh–CA films with hydrogen (600 torr) at 150°C produces small Rh metal particles of ca. 10 Å or less in diameter in CA, which show catalytic activities under mild conditions in various reactions such as hydrogenation of C₂H₄, oxidation of CO, and Fischer–Tropsch type reactions.     

Synthesis and characterization of dense and porous cellulose films

Whereas cellulose‐derived polymers are routinely used as membrane materials, the cellulose polymer itself is not directly used to synthesize dense/porous films for membrane applications. Recently, N‐methylmorpholine N‐oxide (NMMO) and dimethylacetamide (DMAc)/lithium chloride (LiCl) have been successfully employed for dissolving unmodified cellulose. This provides a strong rationale for reexamining the possibility of cellulose membrane fabrication using these solvents. By judiciously selecting solvents, casting conditions, and solvent exchange steps, we successfully synthesized dense/asymmetric‐porous cellulose films. The pore size and porosity of the porous films decreased systematically with increasing cellulose concentration. SEM analysis of the cross sections revealed an asymmetric skinned structure with monotonically increasing pore size away from the skin. The measured pore diameters were in the range 1.8–4.8 μm. Mechanical testing indicated that the dense films possessed tensile properties comparable to those of cellulose acetate (CA) films. Though nitrogen permeability values were comparable for cellulose and CA dense films, cellulose film permeability depended upon the type of drying protocol employed. Overall, these results demonstrate that processability need not be a constraint in the use of cellulose polymer for membrane fabrication. In selected applications, cellulose membranes could become a cost‐effective, environmentally friendly alternative to other more commonly employed membrane polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The chemistry of Pd in cellulose acetate

Pd(OAc)₂ complex has been incorporated in cellulose acetate (CA) as a dispersion medium using cosolvent (THF). The interactions Pd(II) complexes and cellulose acetate are examined by infrared spectroscopy and thermal analysis (DSC). The chemical reactivities of Pd–CA films have been investigated by reacting Pd sites with CO, H₂, O₂, and C₂H₄ in the temperature range 25–150°C and at the pressure of less than 1 atm. Two different Pd-carbonyls and a Pd(O)-hydride species formed in CA are characterized by their infrared spectra. Treatment of 10 wt % Pd–CA films with hydrogen (600 torr) at 70°C produces small Pd metal particles of ca. 30–60 Å in diameter in CA, which show catalytic activities under mild conditions in the reactions such as hydrogenation of C₂H₄ and oxidation of CO.     

Water binding and irreversible dehydration processes in cellulose acetate membranes

The relative amounts of freezing and nonfreezing water in various water-wet cellulose acetate (CA) membranes were determined by NMR techniques, from the initial heights of the water component in the free induction decay (MNR intensity). The results suggest that (1) a significant fraction of the water in various wet CA membranes does not freeze, probably because of strong interaction with the polymer; (2) the relaxation times T₂ of the nonfreezing water are of the order of milliseconds indicating that they are still highly mobile compared with ice; (3) all the water contained in dense CA films or in membranes equilibrated at relative humidity of 0.93 does not freeze upon cooling the membranes from room temperature to ?60°C; (4) the amounts of nonfreezing bound water in membranes is higher than the total amount of water absorbed from liquid water by a dense film of the same polymer. However, the amounts of nonfreezing water in various CA membranes as calculated from the “relative NMR intensities” is substantially lower than those calculated from DSC melting endotherms by assuming the heat of fusion of water in membranes to be identical to that of pure water. Various possible reasons for this discrepancy are discussed. Measurements on the first desorption-adsorption cycle of wet CA membranes have also been performed. They suggest that during the first dehydration process, irreversible changes are induced in the structure of the membrane which result in a significantly lower accessibility of the polymer to interact with water. The extent of these irreversible changes in membrane structure is dependent on the details of the dehydration process being more pronounced at higher temperatures.     

Synthesis and testing of cellulose acetate nicotinate as adsorbent for rhodamine B dye

The esterification of cellulose hydroxyl groups with natural carboxylic acids in mild conditions represents an adequate pathway in obtaining cellulose derivatives with different useful properties. In this article, authors report the synthesis of new mixed ester of cellulose and cellulose acetate nicotinate (CAN) , in a homogenous medium using DMF as solvent, cellulose acetate (CA) as starting cellulosic material, and nicotinic acid as an esterification agent in the presence of p-toluenesulfonyl chloride and pyridine. FTIR and NMR techniques were used to prove the binding of nicotinoyl group at free hydroxyl groups of CA. The obtained CAN was electrospun by electrospinning technique to obtain adsorbent ultrafine fibers, evidenced by SEM images, with high specific surface area. Monolayer Langmuir and empirical Leundrich isotherms were used to assess the adsorption capacity for rhodamine B dye of electrospun CAN in comparison with that of electrospun CA used as starting material. Langmuir isotherm led to a better assessment of experimental data suggesting that the adsorption is mainly determined by hydrogen bonds formed between carboxylic OH hydrogen bonding donor and pyridine N hydrogen bonding acceptor. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47772.     

Space charge limited currents in pure and iodinated cellulose acetate films

Current as a function of voltage has been studied in pure and iodine doped cellulose acetate in the temperature range 313–373 K. The space charge limited currents (SCLC) have been found to exist in pure and doped samples. The temperature dependence of conductivity is found to correspond to two activation energies. The activation energies calculated from conductivity vs. temperature plots for ohmic and SCLC regions were almost equal showing the extrinsic nature of conduction. The break point at 78°C in conductivity vs temperature plots for pure cellulose acetate may correspond to effective glass transition temperature (T′_g). This has been verified from the differential thermal analysis studies. The effect of iodine doping on the electrical conduction in cellulose acetate has been investigated and the results are reported. The infrared studies reveal that iodine stays in the polymer as a neutral molecule and some of which may interact with the polymer molecules.     

Dielectric investigation of isotropic and anisotropic solutions of cellulose acetate in dioxane

The dielectric and optical characteristics of a sample of cellulose acetate (DS = 2.45) in dioxane solutions were studied at 10–50°C of concentration 10–50 wt% to include both isotropic and anisotropic phases. The study showed that the loss maximum, ε_max″, magnitude of polarization, (ε₀ ? ε_∞), static dielectric constant, ε₀, time of relation, (2πf_m)^?1, and refractive index, n_D, steadily increase with concentration up to the critical concentration (41 wt%) and then decrease. The mean-square dipole moment, 〈gμ²〉, decreases steadily up to the critical concentration then remains nearly constant, indicating that the isotropic solution changes to anisotropic, with smaller mean-square dipole moment. Comparison between the results of cellulose acetate (CA) and those of hydroxypropyl cellulose (HPC) reveals that, at the critical concentration in dioxane, the cholesteric structure of HPC possesses a greater mean-square dipole moment with higher temperature coefficient than does CA. The activation energy of the relaxation process for hydroxypropyl cellulose is higher, indicating a greater intrachain interaction compared with cellulose acetate.     

Effect of cellulose acetate/cellulose triacetate ratio on reverse osmosis blend membrane performance

Surface functionalization and modification including the grafting process are effective approaches to improve and enhance the reverse osmosis (RO) membrane performance. This work is aimed to synthesize grafted/crosslinked cellulose acetate (CA)/cellulose triacetate (CTA) blend RO membranes using N-isopropylacrylamide (N-IPAAm) as a monomer and N,N-methylene bisacrylamide (MBAAm) as a crosslinker. The morphology of these membranes was analyzed by scanning electron microscopy and their surface roughness was characterized by atomic force microscopy. The performance of these membranes was evaluated through measuring two major parameters of salt rejection and water flux using RO unit at variable operating pressures. It was noted that the surface average roughness obviously decreased from 148 nm for the pure CA/CTA blend membrane with 2.5% CTA to 110 nm and 87 nm for the grafted N-IPAAm and grafted/crosslinked N-IPAAM/MBAAm/CA/CTA-RO membranes, respectively. Moreover, the contact angle decreased from 51.98° to 47.6° and 43.8° after the grafting and crosslinking process. The salt rejection of the grafted CA/CTA-RO membrane by 0.1% N-IPAAm produced the highest value of 98.12% and the water flux was 3.29 L/m²h at 10 bar.     

Preparation of polyacrylonitrile and cellulose acetate blend fibers through wet‐spinning

Fibers containing both polyacrylonitrile (PAN) and cellulose acetate (CA) were prepared through wet‐spinning by using N,N‐dimethylformamide (DMF) as a solvent. Compatibility of PAN and cellulose acetate blend (PCB) fibers was investigated by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and infrared (IR) spectrophotometry. The absorptive capacity and mechanical properties of the fibers were measured. It was observed that the surface and the cross section of PAN fibers were quite smooth and free from voids and microcracks, whereas cracks and voids were present on the surface and cross section of blend fibers, which increased with the incorporation of CA in the blend. Moisture regains of blend fibers were quite high while their tensile properties showed a partial decrease. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2000–2005, 2007     

Parameters for prediction of reverse osmosis performance of cellulose acetate propionate membranes

Data on reverse osmosis separations have been obtained for 12 alkali metal halide solutes and 24 organic solutes (including eight alcohols, four aldehydes, seven ketones, and five ethers) with cellulose acetate propionate (CAP) membranes using single-solute dilute aqueous feed solutions at 250 psig. From the analysis of these data, the parameters and correlations needed to calculate the values of solute transport parameter D_AM/Kδ for the above classes of inorganic and organic solutes for a CAP membrane of any surface porosity from data on D_AM/Kδ for NaCl only have been generated. These parameters and correlations enable one to predict reverse osmosis separations of different solutes included in the classes of compounds studied in this work, from a single set of experimental data on membrane specifications given in terms of pure water permeability constant and D_AM/Kδ for NaCl. The reverse osmosis characteristics of CAP material lie intermediate between those of cellulose acetate and aromatic polyamide materials reported in the literature.     

Multiphase materials with lignin. XV. Blends of cellulose acetate butyrate with lignin esters

Commercially available cellulose acetate butyrate (CAB, unplasticized) was blended in melt and solution with lignin esters having different ester substituents—acetate (LA), butyrate (LB), hexanoate (LH), and laurate (LL). All lignin esters formed phase‐separated blends with CAB with domain size depending on processing conditions and the interaction between phases depending on blend components. CAB/LA and CAB/LB revealed the strongest interactions with domain sizes on the 15–30 nm scale as probed by dynamic mechanical thermal analysis and differential scanning calorimetry. The glass transitions (T_g) followed the Fox equation. Broader transitions corresponding to the T_gs of the two parent components were observed for CAB blends with LH and LL. Transmission electron micrographs revealed differences in the phase dimensions of the blends in accordance with chemical and processing (i.e., melt vs solvent) differences. Modest gains in modulus were observed for low contents (<20 wt %) of LA and LB. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 448–457, 1999     

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     

Membrane potential measurements on cellulose acetate membranes

Membrane potentials and apparent transport numbers of the cation are reported for cured cellulose acetate membranes bounded by HCl, NaCl, KCl and MgCl₂ solutions, using Ag/AgCl electrodes and a flow-cell method. Membranes cured at 70°, 80° and 90° are used. Bounding solution concentrations vary from 0.005 to 0.05 M at the high concentration side (bounding the dense side of the membrane), and are kept constant at 0.002 M for the low concentration solution. In the KCl 90° membrane case the low concentration solution is varied as well, from 0.0001 to 0.002 M. Results show that cured cellulose acetate membranes are permselective towards univalent cations. This is interpreted as resulting from a low cation-exchange capacity of the dense layer of the cured membrane. The permselectivity increases with increased curing temperature. Addition of a non-electrolyte to the low concentration side reverses the osmotic flow and leads to higher apparent transport numbers of the cation. It is concluded that diffusion in small pores contributes significantly to the transport of ionic solutes through uncompacted membranes.     

Miscible blends of cellulose acetate hydrogen phthalate and poly(vinyl pyrollidone) characterization by viscometry,ultrasound, and DSC

Miscibility characteristics of cellulose acetate hydrogen phthalate (CAP) and poly(vinyl pyrollidone) (PVP) have been investigated by solution viscometric, ultrasonic, and differential scanning calorimetric (DSC) methods. From viscosity measurements, Krigbaum and Wall polymer–polymer interaction parameter Δb was evaluated. Ultrasonic velocity and adiabatic compressibility have been plotted versus blend composition and are found to be linear. Variation of T_g with composition follows Gordon–Taylor equation. T_g values have also been calculated from the Fox equation. The results obtained reveal that CAP forms a miscible blend with PVP in the entire composition range. Compatibility may be due to the formation of hydrogen bonding between the carbonyl group of PVP and the free‐hydroxyl group of CAP. Compatibility has also been confirmed from dielectric measurements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 859–867, 2000