Electrosurface properties of microcrystalline cellulose dispersions in aqueous solutions of aluminum chloride, nitrate, and sulfate

The method of microelectrophoresis is employed to study the dependence of the ζ-potential of microcrystalline cellulose particles on the concentration (10^?6–10^?3 M) and pH (2–11) of aqueous aluminum chloride, nitrate, and sulfate solutions. It is shown that, in the absence of aluminum salts, the isoelectric point (IEP) of the particles is independent on the nature of acid anions and is observed at pH 3.2. The addition of aluminum salts in concentrations as low as 2 × 10 ^?6 M for chloride and nitrate and 1 × 10^?5 M for sulfate causes a shift of IEP to a less acidic region (pH 3.8), the value of which is virtually independent of the nature of the salt. As the concentration of salts is increased, the ζ-potential becomes positive, rises with an increase in pH to a maximum magnitude at pH 5.0–6.0, and decreases further until the second IEP (pH ～ 6.5–7.0) is reached. At higher pH values, the ζ-potential becomes negative again. The observed ζ(pH) dependences are explained by the formation of hydrolyzed aluminum species exhibiting different adsorbabilities on microcrystalline cellulose particles. It is shown that positively charged hydroxocomplexes formed in aluminum sulfate solutions are characterized by a lower adsorbability than hydroxocomplexes formed in chloride and nitrate solutions.     

Aggregation and gelation in hydroxypropylmethyl cellulose aqueous solutions

In this work we present an analysis of the thermal behavior of hydroxypropylmethyl cellulose aqueous solutions, from room temperature to higher temperatures, above gelation. We focus on significant aspects, essentially overlooked in previous work, such as the correlation between polymer hydrophobicity and rheological behavior, and the shear effect on thermal gelation. Micropolarity and aggregation of the polymer chains were monitored by both UV/vis and fluorescence spectroscopic techniques, along with polarized light microscopy. Gel formation upon heating was investigated using rheological experiments, with both large strain (rotational) tests at different shear rates and small strain (oscillatory) tests. The present observations allow us to compose a picture of the evolution of the system upon heating: firstly, polymer reptation increases due to thermal motion, which leads to a weaker network. Secondly, above 55 degrees C, the polymer chains become more hydrophobic and polymer clusters start to form. Finally, the number of physical crosslinks between polymer clusters and the respective lifetimes increase and a three-dimensional network is formed. This network is drastically affected if higher shear rates, at non-Newtonian regimes, are applied to the system.     

The dissolution of microcrystalline cellulose in sodium hydroxide-urea aqueous solutions

It has been reported that cellulose is better dissolved in NaOH-water when a certain amount of urea is added. In order to understand the mechanisms of this dissolution and the interactions between the components, the binary phase diagram of urea/water, the ternary urea/NaOH/water phase diagram and the influence of the addition of microcrystalline cellulose in urea/NaOH/water solutions were studied by DSC. Urea/water solutions have a simple eutectic behaviour with a eutectic compound formed by pure urea and ice (one urea per eight water moles), melting at −12.5 °C. In the urea/NaOH/water solutions, urea and NaOH do not interact, each forming their own eutectic mixtures, (NaOH + 5H₂O, 4H₂O) and (urea, 8H₂O), as found in their binary mixtures. When the amount of water is too low to form the two eutectic mixtures, NaOH is attracting water at the expense of urea. In the presence of microcrystalline cellulose, the interactions between cellulose and NaOH/water are exactly the same as without urea, and urea is not interacting with cellulose. A tentative explanation of the role of urea is to bind water, making cellulose-NaOH links more stable. Member of the European Polysaccharide Network of Excellence (EPNOE),     

Investigation of solubility of microcrystalline cellulose in aqueous NaOH

A cost‐effective and environmentally friendly method to dissolve microcrystalline cellulose (MCC) has been utilized. A detailed investigation of the effects of cellulose amount and solvent (aqueous NaOH) concentration on MCC solubility has been presented. In the experiments, NaOH solutions with concentrations ranging from 3.7 to 18.6 wt% have been employed to dissolve MCC with various weights. The results show that an optimal NaOH concentration range can always be found to give the best solubility of MCC having a certain weight. The solubility monotonically decreases with either the decreasing or increasing of NaOH concentration away from the optimal concentration range. In addition, the optimal concentration range of NaOH for dissolving cellulose has been shown to shrink as the amount of MCC increases. Copyright © 2005 John Wiley & Sons, Ltd.     

Modification of microcrystalline cellulose with pyridone derivatives for removal of cationic dyes from aqueous solutions

Microcrystalline cellulose (MCC) was modified with pyridone derivatives such as pyridone diester (PDE) and pyridone diacid (PDA) by using succinic acid anhydride as a linker. The modified MCCs were characterized by the fourier transform infrared spectroscopy, scanning electron microscopy, thermal gravimetric analysis, elemental analysis and solid state ¹³C NMR. The adsorption capacities of the modified MCCs to cationic dyes were examined by using methylene blue (MB) as a model dye. It was found that the kinetic adsorption data followed the pseudo-second-order kinetic model, and the adsorption equilibriums were reached less than 10 min. The isothermal adsorption data were fitted with the Langmuir isotherm model very well, from which the maximum adsorption capacities of the MCCs modified with PDE and PDA were determined to be 101.01 and 142.86 mg/g, respectively. Further investigation showed that the modified MCCs were pH-dependent for adsorption of MB in aqueous solutions. The modified MCCs could be used for removal of MB from an aqueous solution at pH 8, and reused by regeneration in an acidic solution. It was tested that the modified MCCs had a high reusability for removal of MB from aqueous solutions, and still maintained high adsorption capacities even after multiple cycles of desorption–adsorption processes. Hence, the MCCs modified with PDE and PDA could be an effective and efficient approach to removal of cationic dyes from aqueous solutions.     

Shear rheology of micro-fibrillar cellulose aqueous suspensions

Micro-fibrillar cellulose aqueous suspensions with different fiber lengths were prepared by mechanical refining of softwood pulp fiber suspensions at different specific refining energies. Effects of refining energy level, micro-fiber concentration and temperature on the rheological properties of these aqueous suspensions were studied. These microfibers form a three-dimensional network, which displays typical shear-thinning behavior with little thixotropic tendency, at concentrations as low as 0.5 wt%. A viscoelastic analysis showed that these micro-fibrillar cellulose suspensions at different concentrations (from 0.5 to 2 wt%) exhibit a viscoelastic gel-like behavior [G′ > G″ over an extended range of frequencies (ω) and a weak dependency of G′ on ω] at 25 °C. The storage modulus, G′, at 1 rad/s increased strongly upon increasing concentration from 0.5 to 2 wt% following a power law with an exponent of 3.2. However, increasing the temperature decreases the storage modulus, G′, due to weakening or disruption of intermolecular interactions at elevated temperatures. The viscoelastic behavior changes to liquid-like, with G″ > G′ at the investigated frequency range, for the suspensions at 85 °C.     

Intrinsic viscosity of aqueous suspensions of cellulose nanofibrils

Cellulose nanofibrils (CNF) from wood fibers are of increasing interest to industry because they are from renewable sources and are biodegradable. Owing to their high aspect ratio, they produce viscous suspensions and stiff gels that are strengthened by interfibrillar hydrogen bonds. In this study, the viscosity of aqueous CNF suspensions, at dilute concentrations ( \(nL^{3}<1\) ), was measured at various pH values by addition of HCl, and at various ionic strengths by addition of NaCl and \(\hbox {CaCl}_{2}\) . The results show that the primary electroviscous effect significantly increases the intrinsic viscosity. The intrinsic viscosity under conditions where the surface charge of nanofibrils is fully screened is in good agreement with the predictions of classical theory for dispersions of rodlike particles at low shear rates. Increasing the ionic strength up to \(\kappa d\approx 1\) decreases the intrinsic viscosity; at \(\kappa d>1\) , the intrinsic viscosity increases because of fibril aggregation and increase of the effective volume fraction.     

Aggregation of iron-containing fullerenols in aqueous solutions

Endometallofullerenols Fe@C₆₀(OH)₃₀ were synthesized by a new procedure using a special molecular precursor in the course of electric arc evaporation of a composite carbon electrode. Aqueous solutions of fullerenols Fe@C₆₀(OH)₃₀ were studied by small-angle neutron scattering (SANS) and viscometry under the conditions of transition from dilute to concentrated systems in two media: acidic (pH 3.7) and weakly alkaline (pH 7.8). In a weakly alkaline medium, fullerenols form relatively dense clusters (correlation radius R _C ~ 17 nm), and in acidic medium, less dense structures of size R _C ~ 18 nm in the concentration interval с = 0.5–1.4 wt %. The mechanisms of aggregation of fullerenol molecules in aqueous solutions are discussed. The water-soluble derivatives Fe@C₆₀(OH)₃₀ obtained show promise for biomedical applications in magnetic resonance imaging as contrasting agents that are potentially less toxic than presently used contrasts based on gadolinium chelate complexes.     

Aggregation of rhodamine 3B adsorbed in Wyoming Montmorillonite aqueous suspensions

The adsorption of Rhodamine 3B (R3B) molecules in Wyoming Montmorillonite (Mont) particles suspended in water was studied by electronic absorption spectroscopy. Several adsorbed R3B species in the Mont tactoids were characterized from the observed changes in the absorption spectra by increasing the relative dye/clay concentration and the stirring time of the samples. R3B molecules can be adsorbed as monomeric units both in the water/clay interface and in the interlayer space, and head-to-tail R3B dimers and trimers were present in the external surface of Mont. The formation of internally adsorbed R3B monomers by the migration of the externally adsorbed species to the interlayer space leads to the deaggregation of the dye molecules in the external surface.     

Unique viscoelastic behaviors of colloidal nanocrystalline cellulose aqueous suspensions

Unique rheological and phase behaviors of rod-like nanocrystalline cellulose (NCC) suspensions in aqueous media are revealed in the present article. Specifically, the NCC aqueous suspension remained isotropic in a wide NCC concentration range in which the suspension underwent transition from dilute solution to gel, and the relative viscosity of the NCC suspension could be well fitted by the Sato-Teramoto theory in the full concentration range tested. Correspondingly, both zero-shear viscosity and complex viscosity increased monotonically with NCC concentration, and no maximum value was observed along the curves of zero-shear viscosity or complex viscosity versus NCC concentration, indicating a deviation from the lyotropic system. However, a shear-induced birefringence phenomenon was observed, indicating the NCC suspension formed a temporary ordered structure in the external force field but was unable to form an anisotropic (liquid crystalline) phase. The Cox-Merz rule was not applicable for the NCC suspension as a result of oriented domains, i.e., rod-like NCC particles. Moreover, time-concentration superposition was successfully applied to both the storage and loss modulus, attributed to the isotropic feature of the NCC suspension in the tested concentration range. The reason why this NCC suspension remained isotropic could be because of the strong electrostatic repulsions between NCC particles and the weak tendency or driving force of anisotropy formation as a result of the small aspect ratio of NCC particles, Na⁺ counterions and large amounts of negative charges along the NCC particles. The results suggested that not all the rod-like particles were able to form an anisotropic phase in aqueous suspension, but dominated by various factors.     

The interpretation of X-ray diffraction by aqueous solutions of aluminum(III) nitrate and chromium(III) nitrate

Aqueous solutions of the nitrates of aluminum (0.5 M) and chromium (0.5 M) are investigated with X-ray diffraction at t = 25° C. The experimental intensity is interpreted in terms of an electron product-function which is a sum of various pair contributions. The contribution containing the information about cationic hydration has been evaluated by combining the results of separate experiments. The method is in several aspects quite different from what is usual. Still the results obtained are in general agreement with the data reported elsewhere. That is, sixfold coordination at 1.90 Å and 1.98 Å and a second shell containing about 12 water molecules appearing at 4.10–4.15 Å and 4.20–4.25 Å for Al³⁺ and Cr³⁺ respectively.     

The heat of dissolution of uranyl nitrate in aqueous nitrate solutions

Conclusions A model has been suggested to explain the observed relationship between the measured heats of dissolution of uranyl nitrate in aqueous nitrate solutions and the concentration of the salting-out agent. The model describes the change in the structure of water in the solution with change in its concentration. On the one hand, a destruction of the water structure by ions occurs, which is weakened with increase in the distance from the ion, and leads to such irregularity in the distribution of water molecules in the solution that the mean number of molecules of water in unit volume is increased with increase in the distance from the ions. In experiments on the heat of dissolution this increase leads to increased hydration of the uranyl cation and reduction in the endothermicity of the dissolution with increase in the concentration of the solution. On the other hand, an interaction occurs between the ions of the salting-out agent and the water molecules in the solution, leading to the opposite result: There is an increase in the mean number of water molecules of the solution in unit volume in the direction of these ions. In experiments on the heat of dissolution this is revealed in the dehydration of the uranyl cation, and correspondingly in an increase in the endothermicity of the dissolution with increase in the concentration of the solution. The proposed model is in harmony with data on vapor pressure above the solutions (the relationship between the activity coefficient of the water and the concentration of the solution).Translated from Zhurnal Strukturnoi Khimii. Vol. 3, No. 2, pp. 143–150, March–April. 1962     

Hydrogen bonds and molecular complexes in solutions of cellulose nitrate

Intermolecular hydrogen bonds in the systems based on cellulose nitrate and a number of low-molecular solvents were studied by IR spectroscopy. The majority of the systems under study are characterized only by redistribution of intensities of the spectral bands corresponding to the pure polymer accompanied by their minor shift. In this case, acceptors of cellulose nitrate become sterically accessible for the redistribution of hydrogen bonds, and only an insignificant portion of them forms hydrogen bonds with a solvent. New spectral bands in the IR spectra were observed only for solutions containing diethyldiphenyl carbamide, suggesting the formation of a molecular complex. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 484–487, March, 1999.     

Electroinjection determination of aluminum in aqueous solutions

A procedure is proposed for determining aluminum(III) in water over a concentration range of 0.1–2.0 mg/L in the presence of commensurable amounts of iron(III) using electroinjection analysis. The following parameters were varied in the experiments: the composition and pH of a working buffer solution, the reagent-to-metal concentration ratio, the time of sample injection, the composition of a buffer solution in sample preparation for analysis, the concentration of the reagent (Xylenol Orange), and the reaction time. As a result of this, the sensitivity and selectivity of determining aluminum were improved as compared with the currently available procedures.     

Stability of nanocrystalline cellulose in aqueous KCl solutions

The electrokinetic properties and aggregation stability of nanocrystalline cellulose sols in aqueous KCl solutions have been studied at pH 5.2. Cellulose nanoparticles have been prepared via controlled degradation in a mixture of phosphotungstic and acetic acids. At electrolyte concentrations of <0.01 mol/dm³, the system is stable to aggregation. The experimentally determined threshold of fast coagulation is 0.08 mol/dm³. It has been noted that the structural component of disjoining pressure must be taken into account when considering the aggregation stability of nanocrystalline cellulose sols in terms of the DLVO theory. It has been shown that the sizes of water boundary layers decrease with an increase in the KCl concentration. The effect of medium pH on the electrokinetic potentials and sizes of aggregates has been studied.     

Radiolysis of aqueous solutions of gadolinium nitrate

The specific effect due to Gd³⁺ ion on the radiolysis of aqueous nitrate solutions was determined by measurement of H₂, H₂O₂ and NO ₂ ^– radiolytic yields produced by gamma-irradiation of aerated and deaerated solutions of gadolinium, sodium and calcium nitrates in the concentration range of 10^–5 to 0.3M. Important O₂ consumption in aerated and O₂ evolution in deaerated Gd(NO₃)₂ solutions was found by radiolysis in comparison with the inert cations nitrates. In the former the Gd³⁺ ion generates an O₂ transporter producing an increase in the H₂O₂ yield and a decrease in the NO ₂ ^– yield, while in the latter it enhances the H₂ and NO ₂ ^– production with respect to the same nitrate concentration of the Na⁺ solutions.     

Electrical conductivity and stability of concentrated aqueous alumina suspensions

This work describes the effect of solids load and ionic strength on the electrical conductivity (K(S)) of concentrated aqueous suspensions of commercial alpha-alumina (1-35 vol% solids). The results obtained show that the dependency of the electrical conductivity of the suspending liquid (K(L)) on the volume fraction of solids is well described by Maxwell's model. The change in the conductivity of the suspensions relative to that of the suspending liquid (K(S)/K(L)) was found to be inversely proportional to the solids content, as predicted by Maxwell's model. The relative conductivity rate, DeltaK, could be interpreted in terms of the DLVO theory and the particles double layer parameter, kappaa, and used as a stability criterion. As kappaa changes, in response to the changes in ionic strength, so does the conducting to insulating character of the particles and, as such, their contribution to the overall suspension conductivity (expressed by DeltaK). When the particles become insulating, the suspension conductivity decreases when the solids load increases. The turning point in this particle behaviour corresponds to a critical concentration of ions in the solution that destabilises the suspension and is associated with the critical coagulation concentration (ccc). It is the electrical double layer that ultimately determines the conducting or insulating character of the particles, and that character can be made to change, as required for suspension stability, and accessed by the relative conductivity rate.     

Aggregation behavior of aqueous solutions of ionic liquids

The aggregation behavior in aqueous solutions of three ionic liquids based on the 1-alkyl-3-methylimidazolium cation has been investigated by means of surface tension, conductivity, and small-angle neutron scattering (SANS) measurements. From analysis of the SANS data, models for the shapes and sizes of aggregates have been proposed: the short-chain 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim] [BF4] system can be best modeled by treating it as a dispersion of polydisperse spherical aggregates that form above a critical aggregation concentration, whereas the 1-octyl-3-methylimidazolium iodide, [C8mim] [I], solutions can be modeled as a system of regularly sized near-spherical charged micelles that form above a critical micelle concentration. Solutions of 1-octyl-3-methylimidazolium chloride, [C8mim]-[Cl], display weak long-range ordering of possibly disklike particles culminating in the formation of structures with distinct long-range order at higher concentrations.