Rheological and electron microscopic characterization of aqueous carboxymethyl cellulose gels Part I: Rheological aging of aqueous gels of carboxymethyl cellulose in the free acid form (HCMC)

Aqueous gels of carboxymethylcellulose in the free acid form (HCMC) are obtained when dialyzed sodium carboxymethylcellulose (NaCMC)-gels are treated with a strongly acidic ion exchanger. These gels age rheologically. During the aging process (maximum 60 days), thixotropy and increased viscoelasticity occur. The rheological changes are measured by shear viscosity, coefficient of thixotropy H, complex dynamic shear modulus G^*, shear storage modulusG, shear loss modulusG, and tangent of the phase angle. The aging process is caused by the formation of quasi-crystalline microaggregates of HCMC which can be detected by electron microscopy (Part II).     

Aqueous polysaccharide blends based on hydroxypropyl guar gum and carboxymethyl cellulose: synergistic viscosity and thixotropic properties

Aqueous polysaccharide blends, formed from 2.5% (w/v) solution of hydroxypropyl guar gum (HPG) and 2.5% (w/v) solution of carboxymethyl cellulose (CMC) according to different blending ratios, were investigated at 20 °C in terms of their shear-dependent viscosity and thixotropic properties. The Cross viscosity equation was found to fit the shear-dependent viscosity data with reasonable accuracy. When the HPG solution with the mass fraction (f _HPG) of 0.87 was mixed, the zero shear viscosity (η _o) of the corresponding blend was found to be 168.5753 Pa s, while the η _o values of component HPG and CMC solutions were found to be 3.3859 and 98.6525 Pa s, respectively. For the aqueous HPG/CMC blends investigated, the resulting zero shear viscosity was observed to be much greater than the combined zero shear viscosity of the component polysaccharide solutions, showing a synergistic viscosity property. The quantitative determination of the hysteresis loop area, developed during viscometer tests on shear rate–shear stress reverse paths, was used to describe the thixotropic behavior. When compared with aqueous solutions of the component polysaccharides, these polysaccharide blends could afford enhanced thixotropic property. Maximum thixotropy synergism was observed for the HPG/CMC blend with the f _HPG of 0.67.     

Layer-by-layer assembly of cationic guar gum,cellulose nanocrystals and hydroxypropyl methylcellulose based multilayered composite films

Eco-friendly sustainable materials provide an appealing template to replace contemporary synthetic-nonrenewable resource-based materials while maintaining the acceptable material properties to meet the performance requirements. Here, a layer-by-layer (LBL) self-assembly technique was used for fabricating multilayer composite films using all bio-based polymers/polysaccharides, i.e. cationic guar gum (CGg), carboxylated cellulose nanocrystals (cCNCs) and hydroxypropyl methylcellulose (HPMC). A five layered composite film was fabricated by depositing polymeric layers as follows: CGg→cCNCs→HPMC→cCNCs→CGg. The structural analysis of (CGg/cCNCs/HPMC)_5 L multilayered composite films indicated the existence of electrostatic interaction as well as H-bonding between polymeric layers that resulted in homogenous, dense and compact film surface with improved smoothness and strength properties. As compared to pure CGg film, the (CGg/cCNCs/HPMC)_5 L multilayered composite films showed improved tensile strength (84.8?% increment) and modulus (29.19?% improvement). Importantly, the deposition of HPMC layer contributed in achieving multilayer composite films with more flexible behavior (46.55?% improvement in elongation at break). Furthermore, owing to the high transparency (89.5?% transmittance), appreciable gas and oil barrier performance and resistance to various solvents (e.g. acetone, THF and DMAc), these multilayer films are promising candidates for various applications including renewable/sustainable packaging materials.

     

Rheological behavior and structural interpretation of waxy crude oil gels

A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported.     

Manipulating formation and drug-release behavior of new sol-gel silica matrix by hydroxypropyl guar gum

To develop biocompatible sol-gel silica matrix for the encapsulation of biomolecules or drugs, a novel water-soluble silica precursor, tetrakis(2-hydroxyethyl)orthosilicates (THEOS), was used in combination with a water-soluble polysaccharide derivative, hydroxypropyl guar gum (HPGG). We found that the introduction of HPGG could trigger and accelerate the sol-gel transition of THEOS in water and induce rapid formation of homogeneous gel matrix without the addition of any organic solvents or catalysts. Moreover, added HPGG macromolecules had a great influence on the network structure and particle dimension in the silica gel matrix, as confirmed by scanning electron microscope (SEM) observation. From the time sweep rheological measurements, it was found that a higher HPGG amount could lead to shorter gelation time for the sol-gel transition. From the strain and frequency sweep rheological experiments, it was found that the resultant silica matrix containing a higher amount of HPGG exhibited a narrower linear viscoelastic region, a higher dynamic muduli, and greater complex viscosity. In particular, the gel strength of the silica matrix could be modulated by the amount of HPGG. By investigating the controlled release of vitamin B12 from the sol-gel silica matrixes, a strong dependence of the release profile on the amount of introduced HPGG was observed. In this case, a higher HPGG amount resulted in lower release rate.     

Rheological characterization, crystallization, and gelation behavior of monoglyceride gels

Saturated monoglycerides can form firm gels in water. These gels are networks of stiff plate-like beta-crystals of monoglycerides (a "cardhouse"), grown from a space-filling lamellar liquid-crystalline phase. The molecular mechanism of crystallization is discussed in the light of network formation. The concentration dependence of gel development of (shear-cooled) monoglyceride gels has been studied by rheology. A gelation mechanism has been proposed, consisting of two steps: (i) After formation of a nucleus, rapid crystallization in a lateral direction occurs (probably within one bilayer) by which the first space-filling network is formed. (ii) This is followed by reinforcement of the network by which stacks of crystalline bilayers are formed. The plate-like crystals are linked in connective domains or junction zones, probably containing all the material (cosurfactants, diglycerides, etc.) that does not fit in the crystalline array. Small deformation rheology shows that above about 2 wt% monoglyceride a percolating network is formed. The large deformation rheology is typical for a particle gel with a relatively small strain at failure (both in shear deformation and compression). The connective domains or junction zones already fail when relatively small deformations are put on the system.     

Emulsion stability based on phase behavior in sodium naphthenates containing systems: gels with a high organic solvent content

Addition of heptane to a sodium naphthenates/toluene/water system at 25 degrees C reduces the lamellar liquid-crystal phase range and increases the microemulsion phase range. Both of these effects result in the extension of the composition range where emulsions have low stability. This effect is even stronger at 40 degrees C. Heptane addition also results in the formation of very stable emulsions within the overlapping phase-existence ranges of aqueous (L1) and organic (L2) phases. Stable non-birefringent gel observed in equilibrium with L1 and L2 phases contains only a small percentage of water and sodium naphthenates. The swelling behavior of an unstable gel, an emulsion previously compressed by centrifugation, appears to be due to a stepwise thickening of the thin liquid films between the droplets.     

Enzymatic hydrolysis of native cellulose nanofibrils and other cellulose model films: effect of surface structure

Model films of native cellulose nanofibrils, which contain both crystalline cellulose I and amorphous domains, were used to investigate the dynamics and activities of cellulase enzymes. The enzyme binding and degradation of nanofibril films were compared with those for other films of cellulose, namely, Langmuir-Schaefer and spin-coated regenerated cellulose, as well as cellulose nanocrystal cast films. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the changes in frequency and energy dissipation during incubation at varying enzyme concentrations and experimental temperatures. Structural and morphological changes of the cellulose films upon incubation with enzymes were evaluated by using atomic force microscopy. The QCM-D results revealed that the rate of enzymatic degradation of the nanofibril films was much faster compared to the other types of cellulosic films. Higher enzyme loads did not dramatically increase the already fast degradation rate. Real-time measurements of the coupled contributions of enzyme binding and hydrolytic reactions were fitted to an empirical model that closely described the cellulase activities. The hydrolytic potential of the cellulase mixture was found to be considerably affected by the nature of the substrates, especially their crystallinity and morphology. The implications of these observations are discussed in this report.     

Photo-induced Synthesis and Characterization of Poly（methyl methacrylate） Grafted Sodium Salt of Partially Carboxymethylated Guar Gum

Photo-induced graft copolymerization of methyl methacrylate（MMA） onto sodium salt of partially carboxymethylated guar gum（Na-PCMGG, DS = 0.291） was carried out in an aqueous medium using ceric ammonium nitrate（CAN） as photoinitiator to synthesize a novel graft copolymer, Na-PCMGG-g-PMMA, which may find its potential application as a metal adsorbent. The influences of synthesis variables such as concentrations of photoinitiator（CAN）, nitric acid and monomer（MMA） as well as reaction time, temperature and amount of substrate on the grafting yields were studied and the reaction conditions for optimum photo-grafting were evaluated. At optimum concentration, the maximum values of the grafting yields achieved were G = 271.61% and GE = 63.89%. The experimental results were found to be in very good agreement with the proposed kinetic scheme. The photo-graft copolymerization of MMA onto Na-PCMGG（ DS = 0.291） was also carried out in the presence and absence of ultraviolet radiation for studying the efficiency of the photoinitiator. The influence of carboxymethyl groups introduced onto the guar gum molecules with regard to its behavior towards ultra-violet radiation induced grafting with MMA was also investigated. Photo-grafting process was confirmed and the products were characterized with the help of the spectroscopic（1H-NMR and FTIR） and SEM techniques.     

Dispersion stability and aggregation behavior of TEMPO-oxidized cellulose nanofibrils in water as a function of salt addition

Dispersion stability of TEMPO-oxidized cellulose nanofibrils (TOCNs) in water was investigated through both experimental and theoretical analyses to elucidate the critical aggregation concentration of different salts. The 0.1 wt% TOCN/water dispersions with various NaCl concentrations were evaluated by measuring light transmittance, viscosity under steady-shear flow, and the weight fraction of TOCN that had aggregated. Homogeneous TOCN/water dispersion turned to gel as the NaCl concentration increased. The TOCN dispersion maintained its homogeneous state up to 50 mM NaCl, but aggregated gel particles were formed at 100 mM NaCl. The mixture became separated into two phases (gel and supernatant) at ≥200 mM NaCl. Theoretical analysis using ζ-potentials of TOCN elements in the dispersions revealed that the aggregation behavior upon NaCl addition could be explained well in terms of the interaction potential energy between two cylindrical rods based on the Derjaguin–Landau–Verwey–Overbeek theory. The experiments were extended to analyze critical aggregation concentrations of MgCl₂ and CaCl₂ for the 0.1 wt% TOCN dispersion. In the case of divalent electrolytes, TOCN elements began to form aggregated gel particles at salt concentrations of 2–4 mM, corresponding to the critical aggregation concentration predicted by the empirical Schultz-Hardy rule.     

Effect of fiber drying on properties of lignin containing cellulose nanocrystals and nanofibrils produced through maleic acid hydrolysis

The effect of fiber drying on the properties of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) produced using concentrated maleic acid hydrolysis of a never dried unbleached mixed hardwood kraft pulp was evaluated. Two drying conditions, i.e., air drying and heat drying at 105 °C were employed. It was found that drying (both air and heat) enhanced acid hydrolysis to result in slightly improved LCNC yields and less entangled LCNF. This is perhaps due to the fact that drying modified the cellulose supermolecular structure to become more susceptible to acid hydrolysis and the enhanced hydrolysis severity at the fiber surface when using dried fibers. Drying substantially improved LCNC crystallinity and LCNF suspension viscoelastic behavior. The present study quantitatively elucidated the effect of pulp drying (either air or heat) on producing cellulose nanomaterials and has practical importance because commercial market pulp (heat dried) is most likely to be used commercially.     

Rheological characterization of the dilatant flow behavior of highly substituted hydroxypropylmethyl- cellulose solutions in the presence of sodium lauryl sulfate

 The flow behavior of aqueous solutions of three highly substituted, hydrophobic hydroxypropylmethylcelluloses (HPMC) in mixtures containing the anionic surfactant sodium lauryl sulfate (SLS) was investigated both rheo-mechanically and rheo-optically. For the first time it was possible to demonstrate dilatant flow in these systems, a phenomenon which is otherwise only known of some suspensions and associative thickening solutions. Without addition of SLS, the aqueous HPMC solutions showed the predicted flow behavior of polymer solutions, and the Cox–Merz rule was fulfilled. With the addition of SLS to these HPMC solutions, the least hydrophobic HPMC displayed no dilatancy. The solutions of a more hydrophobic HPMC with SLS exhibited on the one hand an increase in viscosity, and on the other hand shear thinning as well as shear thickening. The most hydrophobic HPMC displayed more clearly the effects of an SLS-dependent viscosity increase and the appearance of dilatant flow. At constant HPMC concentration (0.5% w/w), a maximum increase in viscosity (factor 15) was observed in the critical micelle concentration range for SLS. By rheo-optical measurements it was possible to detect an unusually pronounced alignment of the polymer segments as well as a sharp increase in the birefringence values, even before the macroscopic occurrence of dilatant flow. According to the existing network theories, this behavior of the aqueous solutions of highly substituted HPMCs in mixture with SLS has been interpreted as a shear-induced transition from intra-molecular to intermolecular interactions. Received: 4 February 1998 Accepted: 13 March 1998     

Radiation preparation and swelling behavior of sodium carboxymethyl cellulose hydrogels

Sodium carboxymethyl cellulose (CMC) is a kind of degraded polymer under γ-irradiation. However, in this work, it has been found that CMC crosslinks partially to form hydrogel by radiation technique at more than 20% CMC aqueous solution. The gel fraction increases with the dose. The crosslinking reaction of CMC is promoted in the presence of N₂ or N₂O due to the increase of free radicals on CMC backbone, but gel fraction of CMC hydrogel is not high (<40%). Some important values related to this kind of new CMC hydrogel synthesized under different conditions, such as radiation yield of crosslinking G(x), gelation dose R_g, number average molecular weight of network M_c were calculated according to the Charlesby–Pinner equation. The results indicated that although crosslinked CMC hydrogel could be prepared by radiation method, the rate of radiation degradation of CMC was faster than that of radiation crosslinking due to the character of CMC itself. Swelling dynamics of CMC hydrogel and its swelling behavior at different conditions, such as acidic, basic, inorganic salt as well as temperature were also investigated. Strong acidity, strong basicity, small amount of inorganic salts and lower temperature can reduce swelling ratio.     

Development of sodium alginate-xanthan gum based nanocomposite scaffolds reinforced with cellulose nanocrystals and halloysite nanotubes

Sodium alginate (Alg) and xanthan gum (XG) based nanocomposite scaffolds reinforced with various amounts of cellulose nanocrystals (CNCs) and/or halloysite nanotubes (HNTs) were prepared by freeze-casting/drying method. In this study, the structure-property-performance relationship was mainly focused and analysed. Morphological analysis showed high porosity and pore-interconnectivity (pore channels) in all obtained scaffolds. Structural analysis demonstrates the good interfacial interactions and uniform dispersion of the CNCs and HNTs, involving partial orientation within the polymeric network. The water uptake capacity (from 14.73.7 ± 0.46 g/g to 11.34 ± 0.32 g/g) and porosity (from 91.7 ± 0.81% to 88.5 ± 0.64%) were reduced. The compressive strengths (in dry state from 91.1 ± 1.2 kPa to 114.4 ± 0.6 kPa and in wet state from 9.0 ± 0.8 kPa to 10.6 ± 0.8 kPa), thermal stability, cytocompatibility (MC3T3-E1 osteoblastic cells) of the nanocomposite scaffolds improved as compared to Alg and AlgX scaffolds without CNCs and/or HNTs. The obtained scaffolds may be appropriate as scaffolding material in bone tissue engineering.     

Rheological and electron microscopic characterization of aqueous carboxymethyl cellulose gels Part II: Visualization of the gel structure by freeze-fracturing

The spatial structure of gels of sodium carboxymethyl cellulose (NaCMC-gel) and carboxymethyl cellulose in the free acid form can be imaged in the transmission electron microscope (TEM). The freeze-fracturing technique is suitable for this. Experiments with test preparations (10 % aqueous glycerol solution) show that cooling rates during freeze-fixing are decisive for visualization, and that cooling rates can be improved substantially by using a cryojet. The increase of the cooling rate to more than 15 000 K/s makes it possible to obtain extremely fine network structures with a mesh width of 5–25 nm and with a filament thickness of 2–3 nm. The results obtained after jet-freezing show differences in the structure of the two gels: quasi-crystalline microaggregates in the HCMC-gel can be seen, and they cause an increased elasticity and opalescence of the aged HCMC-gels.     

Preparation and characterization of cross-linked guar gum microspheres: optimization using factorial design

In the present work cross-linked guar gum microspheres were prepared for colon specific delivery of ornidazole. Development and optimization of guar gum microspheres for colonic drug delivery was carried out using a 2(4) factorial design based on four independent variables. Microspheres were prepared by emulsification method using glutaraldehyde as cross-linking agent. Morphology and surface characteristics of the formulations were determined by scanning electron microscopy. Particle size of the guar gum microspheres was determined by particle size analyzer. In vitro drug-release studies were performed in conditions simulating stomach-to-colon transit in the presence and absence of rat cecal contents. Only a small fraction of drug was released at acidic pH; however, the release of drug was found to be higher in the presence of rat cecal contents, indicating the susceptibility of guar gum matrix to colonic enzymes released from rat cecal contents. The significance of differences was evaluated by analysis of variance (ANOVA). Differences were considered statistically significant at p<0.05.     

Fabrication and stimuli response of rice husk-based microcrystalline cellulose particle suspension under electric fields

We report on the electro-responsive electrorheological (ER) properties of microcrystalline cellulose (MCC) particles. It was synthesized from raw rice husk (Downes Rice) through the 3-step preparation of alkali treatment, bleaching, and hydrolysis. The MCC particles with mean particle size about 26 μm were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analysis. The MCC particles were then dispersed in silicone oil to create an ER fluid; its dramatic electro-responsive phase changes under an applied electric field were observed by an optical microscopy. The effect of electric field strengths on ER performances of the ER fluid were determined using a rotational rheometer equipped with a high-voltage generator from the controlled shear rate mode and dynamic oscillation measurements. The fluid showed typical ER effects of Bingham fluid behavior with yield stress and viscoelastic properties under an applied electric field.     

Thermal and mechanical behavior of biodegradable polyester films containing cellulose nanofibers

Journal of Thermal Analysis and Calorimetry - Agricultural waste is a valuable source of advanced materials. Cheap nanocellulose may be obtained from plum shells agricultural residues and further...     

Properties of films, solutions, and gels prepared from sodium carboxymethyl cellulose blends with synthetic polymers

An extremal dependence of the intrinsic viscosity of poly(vinyl alcohol) blends with sodium carboxymethyl cellulose and polyacrylamide on composition has been established. A correlation between the viscosity properties of solutions and mechanical properties of films made of sodium carboxymethyl cellulosepoly(vinyl alcohol) blends is observed that is indicative of the interpolymer interaction in these systems. The obtained regularities can be used to produce high-modulus coordination-crosslinked gels based on these blends.