Rheology of a cellulose graft copolymer. Comparison with other closely packed gel thickeners

Hydrolyzed cellulose–polyacrylonitrile graft copolymer is a polyelectrolyte gel suspension with a high viscosity in water. It is a closely packed swollen gel particle suspension in the appropriate concentration range and has similar rheological properties to other thickeners of this type. Viscosities η in either water or salt solution are reduced to a single master curve by use of the reduced viscosity function η/cQ, where c is weight fraction of polymer and Q is swelling volume in excess solvent of the same ionic strength. The effective molecular weight between crosslinks, M_c, determined from shear modulus, corresponds to M_c values for other closely packed gel thickners of similar η/cQ. Among all examples of this class of thickener, the plateau values of η/cQ, which occur at cQ > 2, are approximately inversely proportional to M_c.     

Diffusion/adsorption model of cellulose dyeing. II. Ordinary cellulose–direct dye system

The diffusion and adsorption of C.I. Direct Yellow 12 and Blue 15 in water-swollen ordinary cellophane sheets were examined at various ionic strengths. The concentration dependence of apparent diffusion coefficients, D_c, for these dyes was obtained from the diffusion profiles in the substrate, which were measured by the use of the cylindrical film roll method. The decrease of apparent porosity with an increase in the amounts of adsorption was observed. To explain the diffusion/adsorption behaviors of these systems, a variable porosity model was proposed and was applied to analyze the concentration dependence of D_c's. The diffusion/adsorption behaviors of these dyes could be quantitatively described by this model at relatively low ionic strengths. At higher ionic strengths and/or lower values of C, i.e., at the large values of C_im/C_m, where the C's are the concentrations of immobilized (suffix im) and mobile (suffix m) species, it needed to introduce the concept of dynamic equilibria which occurred simultaneously with diffusion but deviated from the true equiliblia measured by the adsorption experiments.     

Polymer rheology: Influence of molecular weight and polydispersity

Literature data on the non-Newtonian flow of bulk polymer and of polymer solutions are correlated on the basis of a four-parameter equation, η = η_∞ + (η₀ ? η_∞)/[1 + (τD)^m], η being the viscosity at shear rate D, and η₀ and η_∞ limiting values at D = 0 and D = ∞, respectively. The parameters η₀, η_∞, and τ all show dependence on molecular weight, and in general there is good correlation between τ and η₀. There is evidence that τ is related to a molecular weight higher than the weight-average. The exponent m shows dependence on molecular weight distribution and approaches an upper limit of unity for a monodisperse linear polymer. For linear unblended polymers it may be expressed empirically by m = (M?_n/M?_w)^1/5.     

Nanoindentation creep and glass transition temperatures in polymers

The nanoindentation creep behaviour of several different polymers has been investigated. The extent of creep ε is represented by the Chudoba and Richter equation: ε = ε_eln(ε_rt + 1), where t is the loading time and ε_e and ε_r are material constants. Creep was determined in this way for a variety of polymers at T_exper = 301.7 K. Some of the materials studied were far above, some far below and some near their glass transition temperatures T_g. The creep rate ε_r was plotted as a function of y = (T_g ? T_exper); a single curve was obtained in spite of a large variety of chemical structures of the polymers. The ε_r = ε_r(y) diagram can be divided into three regions according to the chain mobility. At large negative y values, the creep rate is high due to the liquid‐like behaviour. At large positive y values in the glassy region, the creep rate is higher than that in the negative y‐value region; the creep mechanism is assigned to material brittleness and crack propagation. In the middle y range there is a minimum of ε_r. These results can be related to glassy and liquid structures represented by Voronoi polyhedra and Delaunay simplices. The latter form clusters; in the glassy material there is a percolative Delaunay cluster of nearly tetrahedral high‐density configurations. The creep mechanism here is related to crack propagation in brittle solids. In the liquid state there is a different percolative Delaunay cluster formed by low‐density configurations, which, as expected, favour high creep rates. Copyright © 2007 Society of Chemical Industry     

Study of viscosity abnormality of PS/toluene solution in extremely dilute concentration regime

The concentration dependence of the reduced viscosity η_sp/c and the translational diffusion coefficient D as well as the radius of gyration R_g of polystyrene in toluene were studied by viscometry and laser light scattering (LLS), respectively. The influence of the experimental error on the determination of the η_sp/c was investigated and a quantitative relation was given out. Viscometric experiment found that the η_sp/c–c curve is clearly divided into two parts by dynamic contact concentration c_s. When c > c_s, it shows normal linearity as predicted by Huggins equation. But when c < c_s, i.e., in the extremely dilute regime, the η_sp/c–c curve is no longer linear and levels off considering the experimental uncertainty. This new finding was confirmed by the following LLS experiment, which indicates that the size of the polymer chains no longer varies with concentration when c < c_s. As a result, we, for the first time, using the method of combination of viscometry and LLS, prove an important conclusion that in the extremely dilute concentration regime, the reduced viscosity of polymer solution, at least for PS/toluene, conforming to the Einstein viscosity equation is just the intrinsic viscosity and independent of the concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4440–4446, 2006     

Dehydration of THF‐water mixtures using zeolite‐incorporated polymeric membranes

Using a solution technique, polymeric composite membranes were prepared by the incorporation of NaY zeolite into chitosan. The resulting membranes were tested for pervaporation separation of water–tetrahydrofuran mixtures in a temperature range of 30–50°C. The effect of membrane swelling on the separation performance was studied by varying the water composition in the feed from 5 to 30 mass %. Pervaporation data demonstrated that both flux and selectivity increased simultaneously with increasing zeolite content in the membrane. This was explained on the basis of enhancement of hydrophilicity, selective adsorption, and establishment of molecular sieving action. It was found that both total flux and flux of water are close to each other, suggesting that the developed membranes are highly selective toward water. The membrane containing the highest loading of zeolite exhibited the highest separation selectivity of 2140 with a substantial water flux of 16.88 × 10^?2 kg/(m² h) at 30°C for 5 mass % of water in the feed. From the temperature dependency of diffusion and permeation data, the Arrhenius activation parameters were estimated. A significant difference was noticed between E_pw and E_pTHF, E_Dw and E_DTHF values, signifying that membranes developed with higher loading of zeolite exhibited remarkable separation selectivity toward water. The E_p and E_D values ranged between 11.69 and 21.23, and 11.21 and 20.72 kJ/mol, respectively. All the membranes exhibited positive ΔH_s values, suggesting that the heat of sorption is still dominated by Henry's mode of sorption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Rheology and water swelling of carboxymethyl starch gels

A series of gels differing in ionic content was prepared by derivatizing starch with varying amounts of carboxymethyl add-on. Some derivatives were lightly crosslinked with epichlorohydrin to reduce soluble material and increase the amount of gel. The gel fraction of each batch was isolated, and viscosity η, shear modulus G, and swelling in water and salt solution were then determined. One gel suspension, examined in more detail, was demonstrated to behave as a closely packed gel thickening agent, thereby warranting use of the three reduced functions: reduced concentration cQ (c is weight concentration of polymer, Q is swelling capacity in excess fluid), η/cQ, and G/c^1/3. At cQ greater than about 2, η/cQ, and G/c^1/3 reach constant plateau values, as is typical of other examples of closely packed gel thickeners. In a comparison among the gel suspensions, plateau values of the reduced viscosity function were nearly proportional to the apparent crosslink density G/c^1/3, in agreement with other closely packed gel thickeners, but were not affected by ionic content of dry polymer. The water swelling capacities of the different gels ranged from 47 to 150 g/g and were correlated with both ionic contents and apparent crosslink densities, but the effects of these variables were less than suggested by theory.     

Stress relaxation of elongated strip of poly(vinylidene fluoride) in ethyl acetate vapor

Poly(vinylidene fluoride) films in ethyl acetate vapor were studied at 30°C for vapor pressures of p = 0, 12, 30, 40, 66, 85 torr and elongations ε = 4.5%, 7%, 9.5%, 19%, 29%, and 44%. A cyclic experiment was also performed at ε = 7% and p = 40 torr for three sorption/desorption cycles. Assuming, as a first approximation, that the stress relaxation of the “dry” and “wet” polymers is proportional to the elastic strain, ε_el, empirical calculations were performed and compared to experimental results. In general, the presence of a vapor or gas in a polymer matrix enhances the stress relaxation by softening or plasticizing the polymer and transforming a portion of the elastic strain, ε_el, into the plastic strain, ε_pl. As the transformation continues, the sorption and stress of the wetted elongated sample change simultaneously with time until an optical “overshoot” and a mechanical or stress “undershoot” is observed. This result seems to be the consequence of the differential change of the stress of the “dry” and “wetted” samples with sorption time, τ = t ? t_o(t = time; t_o = initial sorption time), which depends on the differential time dependencies of the transformations of the elastic and plastic strains.     

Dialdehyde polyethylene glycol cross-linked poly(vinyl alcohol) membranes with enhanced CO2/N2 separation performance

The development of carbon dioxide (CO₂) separation technology is crucial for mitigating global climate change and promoting sustainable development. In this study, we successfully synthesized an array of cross-linked poly(vinyl alcohol) (PVA) membranes, xALD-PEG-ALD-c-PVA, with enhanced CO₂/N₂ separation performance by employing dialdehyde polyethylene glycol (ALD-PEG-ALD) as a cross-linker. The formation of the cross-linked network structure not only inhibits the crystallization of PVA but also disrupts hydrogen bonding and thus increases fractional free volume of PVA chains. Under the synergistic effect of these multiple factors, the cross-linked PVA membranes exhibit a significantly improved CO₂ permeability. Moreover, they maintain high CO₂/N₂ selectivity, attributing to the CO₂-philic characteristic of ethylene oxide groups in the cross-linked structure. At the ALD-PEG-ALD content of 1.6 mmol g⁻¹, the xALD-PEG-ALD-c-PVA membrane demonstrates a CO₂ permeability of 41.4 barrer and a CO₂/N₂ selectivity of 57.4 at 2 bar and 25°C. Furthermore, compared with the pristine PVA membrane, xALD-PEG-ALD-c-PVA membranes manifest superior mechanical properties and outstanding separation performance for a CO₂/N₂ (15/85, vol%) gas mixture. The excellent combination of permeability and selectivity makes xALD-PEG-ALD-c-PVA membranes highly promising for various CO₂ separation applications.     

Viscometric study of extremely dilute macromolecular solutions: Critical concentration c and the intrinsic viscosity of the polystyrene through scaling laws. The values of the Huggins constant

A crossover is observed in the variation of the reduced viscosity, η_sp/c, as a function of the concentration, c, for polystyrene solutions in cyclohexane and dioxane. This crossover is attributed to the critical concentration c at which the macromolecular coils start to contact. The critical concentration c is related to the molecular weight and the intrinsic viscosity of the polystyrene through scaling laws. The values of the Huggins constant k' determined in the concentration regions below c (extremely dilute solutions) confirm the Peterson-Fixman theory.     

Modification of tetraethylorthosilicate crosslinked poly(vinyl alcohol) membrane using chitosan and its application to the pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate crosslinked poly(vinyl alcohol) membrane was modified by varying the amounts of chitosan. The resulting membranes were characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry. The effects of chitosan content and feed composition on the pervaporation performance of the membranes were analyzed. The modified membranes exhibit simultaneous increase of both flux and selectivity. The membrane containing 15 mass % of chitosan shows the highest separation selectivity of 2991, with a flux of 2.39 × 10^?2 kg/(m² h) at 30°C for 10 mass % of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that the membranes could be used effectively to break the azeotropic point of water–isopropanol mixture, so as to remove water from the isopropanol. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are significantly lower than those of isopropanol permeation (E_pIPA), suggesting that the membranes developed here have higher separation ability for water–isopropanol system. In addition, difference was negligibly small between the activation energy values of total permeation (E_p) and water permeation (E_pw), indicating that coupled transport is minimal because of a higher selective nature of membranes. The E_p and E_D values ranged between 40.92 and 52.60, and 39.58 and 52.47 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values observed in all the membranes suggests that Henry's mode of sorption is predominant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1380–1389, 2006     

Comparison of mechanical properties of compacted calcium hydroxide and portland cement paste systems

Mechanical properties of Ca(OH)₂ are compared with those of portland cement paste at different porosities. Intrinsic values of modulus of elasticity (E) and microhardness (H) for Ca(OH)₂ compacts were obtained by extrapolating to zero porosity log E and log H versus porosity curves. The values for the Ca(OH)₂ and portland cement paste systems are of similar magnitude. Flexural strength values for both systems were also determined to be of similar magnitude for the porosity range studied. Fracture terms (K_c, J_c, G_c, Y_T) were determined. K_c and Y_T versus porosity plots for both systems revealed that these fracture terms are of similar magnitude in the porosity range common to both.     

Preparation of zeolite‐incorporated poly(dimethyl siloxane) membranes for the pervaporation separation of isopropyl alcohol/water mixtures

ZSM‐5 zeolite‐incorporated poly(dimethyl siloxane) membranes were prepared, and the molecular dispersion of the zeolite in the membrane matrix was confirmed with scanning electron microscopy. After the swelling of the membranes was studied at 30°C, the membranes were subjected to the pervaporation separation of isopropyl alcohol/water mixtures at 30, 40, and 50°C. The effects of the zeolite loading and feed composition on the pervaporation performances of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the membrane matrix. This was examined on the basis of the enhancement of hydrophobicity, selective adsorption, and the establishment of molecular sieving action. The membrane containing the highest zeolite loading (30 mass %) had the highest separation selectivity (80.84) and flux (6.78 × 10^?2 kg m^?2 h^?1) at 30°C with 5 mass % isopropyl alcohol in the feed. From the temperature dependence of the diffusion and permeation values, the Arrhenius activation parameters were estimated. A pure membrane exhibited higher activation energy values for permeability (E_p) and diffusivity (E_D) than zeolite‐incorporated membranes, and signified that permeation and diffusion required more energy for transport through the pure membrane because of its dense nature. Obviously, the zeolite‐incorporated membranes required less energy because of their molecular sieving action, which was attributed to the presence of straight and sinusoidal channels in the framework of the zeolite. For the zeolite‐incorporated membranes, the activation energy values obtained for isopropyl alcohol permeation were significantly lower than the water permeation values, and this suggested that the zeolite‐incorporated membranes had higher selectivity toward isopropyl alcohol. The E_p and E_D values ranged between 21.81 and 31.12 kJ/mol and between 15.27 and 41.49 kJ/mol, respectively. All the zeolite‐incorporated membranes exhibited positive values of the heat of sorption, and this suggested that the heat of sorption was dominated by Henry's mode of sorption. sorption. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1377–1387, 2005     

Preparation and characterization of pH-sensitive,interpenetrating networks of poly(vinyl alcohol) and poly(acrylic acid)

Hydrogels with varying cross-linking ratio and ionic content were prepared from interpenetrating networks of poly(vinyl alcohol) and poly(acrylic acid). Equilibrium swelling studies were conducted and the average molecular weight between cross-links, M _c, and mesh size were determined. Hydrogels with large M _c, values were found to swell to a greater extent than those with small M _c values. It was also observed that an increase in M _c yielded faster swelling and deswelling rates, as the rates for membranes with M _c = 18,000 were about twice as fast as were the rates for membranes with M _c = 34,000. Oscillatory swelling behavior was investigated in response to changes in the pH and ionic strength of the swelling medium. A change in pH from 3 to 6 caused an ionization of the hydrogels and an increase in the weight swelling ratio, with a greater increase exhibited by IPNs with a higher ionic content. Increase in pH also caused an increase in the average mesh size. © 1995 John Wiley & Sons, Inc.     

Investigation on the effects of fabrication parameters on the structure and properties of surface‐modified membranes using response surface methodology

Surface Modifying Macromolecules (SMM) were used to alter the hydrophobicity of polyetherimide (PEI) hollow fiber membranes and the effects of three fabrication parameters, which are the mass fraction of PEI and SMM in the casting dope and air gap, on the properties of fabricated membranes were investigated by application of Response Surface Methodology (RSM). The fabricated membranes were characterized in terms of mean pore size (r_P,m), permeation rate of helium gas at 1 bar transmembrane pressure difference, membrane porosity, and contact angle of water with inner and outer surfaces of membrane. The regression models obtained for mean pore size and permeation rate have good statistical parameters and are accurate. The model for r_P,m predicts that plot of r_P,m versus air gap has a minimum point, whereas the plots of r_P,m versus PEI (wt %) and SMM (wt %) have maximum points. The regression model developed for membrane porosity predicts that membrane porosity decreases when air gap increases. Since water was used as bore fluid, the model developed for inner surface contact angle has low accuracy but the model developed for outer surface contact angle predicts that contact angle increases with SMM concentration in dope solution but there is a maximum point versus air gap. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Gas permselection properties in silicone-coated asymmetric polyethersulfone membranes

The gas permeation properties of H₂, He, CO₂, O₂, and N₂ through silicone-coated polyethersulfone (PESf) asymmetric hollow-fiber membranes with different structures were investigated as a function of pressure and temperature and compared with those of PESf dense membrane and silicone rubber (PDMS) membrane. The PESf asymmetric hollow-fiber membranes were prepared from spinning solutions containing N-methyl-2-pyrrolidone as a solvent, with ethanol, 1-propanol, or water as a nonsolvent-additive. Water was also used as both an internal and an external coagulant. A thin silicone rubber film was coated on the external surface of dried PESf hollow-fiber membranes. The apparent structure characteristics of the separation layer (thickness, porosity, and mean pore size) of the asymmetric membranes were determined by gas permeation method and their cross-section morphologies were examined with a scanning electron microscope. The results reveal that the gas pressure normalized fluxes of the five gases in the three silicone-coated PESf asymmetric membranes are nearly independent of pressure and did not exhibit the dual-mode behavior. The activation energies of permeation in the silicone-coated asymmetric membranes may be larger or smaller than those of PESf dense membrane, which is controlled by the membrane physical structure (skin layer and sublayer structure). Permselectivities for the gas pairs H₂/N₂, He/N₂, CO₂/N₂, and O₂/N₂ are also presented and their temperature dependency addressed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 837–846, 1997     

Crazing in glassy polymers: Studies on polymer-glass bead composites

Stress-strain curves of glass bead-filled glassy polymers show a slope discontinuity related to crazing in the matrix. This discontinuity serves as basis for a simple method for determining ε_p′ the critical strain in the polymer to initiate crazing. The stress at the discontinuity (σ_D) is governed by the nature of the dispersed particles acting as stress concentrators. The two parameters, ε_p′ and σ_D, (neither of which is a function of the filler content) have the following values in ascending order σ = 1540, 1750, 1880, 2390 and 3300 psi for polystyrene, ABS, poly(vinyl chloride), SAN and poly(phenylene oxide) respectively; ε_p = 0.63, 0.72, 0.81, 1.10 and 1.67 percent for poly(vinyl chloride), polystyrene, SAN, ABS and poly(phenylene oxide) respectively. In coupled particulate systems, (σ_D) is increased and apparently vaies with the efficiency of the coupling agent. The modulus of a particulate system can be predicted by a one-parameter equation.     

Effects of ionic strength and pH on the diffusion coefficients and conformation of chitosans molecule in solution

The effects of ionic strength and pH on the diffusion coefficients and gross conformation of chitosan molecules in solution were studied. Chitosan with 83% degree of deacetylation (DD) was prepared from red shrimp (Solemocera prominenitis) processing waste. Ten different molecular weight chitosans were prepared by ultrasonic degradation, and their molecular weights were determined by static light scattering. The weight-average molecular weight (M_w) were between 78 to 914 kilo dalton (KDa). Solution of different ionic strengths (I = 0.01, 0.10, and 0.20) but the same pH (2.18) and different pHs (2.37, 3.10, and 4.14) but the same ionic strength (I = 0.05) were prepared to measure their mutual diffusion coefficient (D_m). The diffusion coefficients for standard condition (D_20,w) were derived from D_m. Intrinsic viscosities ([η]) were determined by a capillary viscometer in different pH solutions. The Mark–Houwink exponents a and ε were obtained from plots of Log [η] and Log D_20,w versus Log M_w, respectively. The results show that diffusion coefficients increased with increasing ionic strength or with increasing pH or with decreasing M_w. Value of ε and a were between 0.503 to 0.571 and ranged from 0.543 to 0.632, respectively. The results indicates that chitosans conformation were in random coil in solutions in the ranges of ionic strength and pH studied. The values of a*, ε* and a**, ε**, Mark–Houwink exponents of smaller and higher than 223 KDa chitosans, respectively, were between 0.752 to 0.988 and 0.585 to 0.777 for smaller M_w chitosans and 0.406 to 0.428 and 0.430 to 0.518 for larger M_w chitosans, respectively. Molecular-weight-induced conformational transition occurred because smaller M_w chitosans was more extended than higher M_w chitosans. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2041–2050, 1999     

Preparation and characterization of melt-stretched polypropylene–polypropylene-g-poly(α-methyl styrene-co-glycidyl methacrylate-co-γ-methacryloxypropyl trimethoxy silane)–silicon dioxide compound microporous membranes

Polypropylene (PP)–silicon dioxide (SiO₂) compound microporous membranes were fabricated by a melt-stretching method. Although the permeability, porosity, and hydrophilicity values of the microporous membranes were found to be highest at an SiO₂ content of 2 wt %, the heat resistance of the membranes was relatively low. To improve the heat resistance of the microporous membranes, a macromolecular coupling agent, PP-g-poly(α-methyl styrene-co-glycidyl methacrylate-co-γ-methacryloxypropyl trimethoxy silane) (PAGK), was introduced into the membrane. In the PP–PP-g-PAGK–SiO₂ composite systems, the content of SiO₂ was controlled at 2 wt %, and the proportion of PP-g-PAGK was varied. With increasing PP-g-PAGK content to 0.6%, the Gurley value decreased from 250 to 239 s, and the porosity increased from 50.8 to 51.6%. The hydrophilicity of the microporous membranes increased with the incorporation of PP-g-PAGK, and their water vapor transmission rate reached a maximum of 3360 g m⁻²/24 h at a PP-g-PAGK content of 0.6%. The heat resistance of the PP–PP-g-PAGK–SiO₂ compound microporous membranes was slightly higher than that of the pure PP microporous membrane. Additionally, the cycle performance of a cell assembled with the PP–PP-g-PAGK–SiO₂ membrane was better than that constructed with the pure PP membrane. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47937.