Viscoelastic properties of dibenzylidene sorbitol (DBS) physical gels at high frequencies

The rheological behavior of Dibenzylidene D-Sorbitol (DBS) gels formed in ethylene glycol, glycerol, mineral oil, ethanol, and chlorobenzene was studied using oscillatory squeezing flow viscometry. The storage (G ^′) and loss (G ^″) moduli were measured as a function of gellant concentration (0.5–2 w/w) and type of solvent. As expected greater values of gel strength (G ^′) were observed for gels containing higher concentrations of DBS. In addition, both storage and loss moduli of 2% systems were mostly frequency independent over the studied range, whereas 0.5% gels did exhibit some degree of dependence. We also found that the solvent plays an important role in the properties of the gels. Among the parameters that affect the viscoelastic properties of DBS gels, the solvent polarity and its ability to form hydrogen bonding may have significant effects on the gel rheology.     

Rheological and diffusion properties of a dextran-con A polymer in the presence of Insulin and Magnesium

Previous work carried out in our laboratories has focused on the formation and investigation of a dextran and concanavalin A (con A) based gel, which has the ability to alter its conformational structure in the presence and absence of free and terminal glucoses such that a gel–sol phase transition occurs. Here we report the diffusion and rheological investigations in to the effects of the addition of insulin and varyingconcentrations of magnesium chloride hexahydrate (Mg₂Cl₂6H₂O) at 20 and 37 °C. Rheological examination of glucose-sensitive (dextran-con A) gels were conducted using a cone and plate viscometer used in continual rotation and oscillatory modes. The results are interpreted in terms of the structure of the gel network and suggest rheological assessment provides an effective method of assessing the properties of gel systems. The subsequent testing of such formulations in in-vitro diffusion experiments revealed a reduction in the rate of diffusivity in the insulin marker, poly R-478 dye. The performance of this self-regulating drug delivery system has been examined and the addition of insulin and magnesium chloride may alter the way in which the gel operates as a drug delivery device and in the delivery of insulin. This may have implications for other ligands.     

Characterization of polyacrylamide gels as an elastic model for food gels

Serving as an elastic model system for food gels, characteristics of polyacrylamide (PAAm) gels were investigated using small amplitude and large deformation rheological tests. The PAAm gels displayed elastic or viscoelastic behavior depending on network crosslink density. For elastic PAAm gels, the rheological properties obeyed the theory of rubber elasticity; whereas for viscoelastic PAAm gels, shear modulus depended on temperature. The elastic PAAm gel fracture parameters did not change with deformation rate (0.2–5.5 s^–1), indicating insignificant viscous flow during deformation. Fracture stress was correlated with gel monomer concentration, whereas the fracture strain remained constant regardless of the monomer concentration. In addition, the stress was linearly proportioned with strain up to fracture, indicating that PAAm gels did not experience finite network chain extensibility during large deformation. Consequently, the fracture of PAAm gels did not result from the extensional limitation of network chains, nor did gel fracture result from the nonlinear force–distance relationship between polymer connections. Purportedly, the fracture of PAAm gels was caused by external force overcoming the gel cohesive forces, and low strength of PAAm gels compared to rubbers caused fracture prior to experiencing nonlinear stress-strain deformation.Paper No. FSR04-20 of the Journal Series of the North Carolina Agricultural Research Service, Raleigh, NC 27695-7643. The use of trade names does not imply endorsement by the North Carolina Agricultural Research Service of products named, nor criticisms of similar ones not mentioned.     

Rheological behavior of suspensions of modified and unmodified cellulose nanocrystals in dimethyl sulfoxide

The rheological behavior of cellulose nanocrystal (CNC) and modified CNC (mCNC) suspensions in dimethyl sulfoxide (DMSO) was investigated. The efficiency of the surface modification of CNCs by grafting an organic acid chloride to produce hydrophobic CNCs has been verified by X-ray photoelectron spectroscopy (XPS). The thermal degradation temperature of the mCNCs was found to be 165 versus 275 °C for CNCs. The CNC suspensions in DMSO at 70 °C underwent gelation at very low concentration (1 wt%) after 1 day. The network formation was temperature sensitive and did not occur at room temperature. For gels containing 3 wt% CNCs, the complex viscosity at 70 °C increased by almost four decades after 1 day. For the mCNCs in DMSO, a weak gel was formed from the first day and temperature did not affect the gelation. Finally, the effect of adding 10 wt% of polylactide (PLA) to the solvent on the rheological properties of CNC and mCNC suspensions was investigated. The properties of suspensions containing 1.9 wt% CNCs and mCNCs increased during the first and second days, and PLA did not prevent gel formation. However, the reduced viscosity and storage modulus of the CNC and mCNC gels with PLA were lower than those of samples without PLA.     

Structure development during crystallization of polycaprolactone

In this paper, the quiescent crystallization of polycaprolactone (PCL) melts is studied by rheological measurements coupled to calorimetry and optical microscopy. Based on a comparison between the different techniques, we find that the increase in viscoelastic properties during crystallization starts only when a relatively high degree of crystallinity is reached, which corresponds to a much developed crystalline microstructure. Like other semicrystalline thermoplastic polymers, the crystallization of PCL can be seen as a gelation process. In this case, however, we find a peculiar critical gel behavior, as the liquid-to-solid transition takes place at a very high (~20%) relative crystallinity, and this value is independent of temperature. These facts, and the comparison with optical microscopy observations, suggest that the microstructure at the gel point is controlled by the interactions between the growing crystallites. The gel time (from rheometry) and the half-crystallization time [from differential scanning calorimetry (DSC)] both show an Arrhenius-like behavior and have the same pseudoactivation energy. A practical implication of this parallel behavior of t _gel and t _0.5 is that the rheological measurements can be used to extend to higher temperatures the study of crystallization kinetics where DSC is not sufficiently sensitive.This paper was presented at the second Annual European Rheology Conference (AERC) held in Grenoble, France, 21–23 April 2005.     

Rheological properties of poly(vinyl chloride)/plasticizer systems—relation between sol–gel transition and elongational viscosity

Poly(vinyl chloride) (PVC)/di-isononyl phthalate systems with PVC content of 45.5 (PVC8) and 70.4 wt% (PVC6) were prepared by a hot roller at 150 °C and press molded at 180 °C. The dynamic viscoelasticity and elongational viscosity of PVC8 and PVC6 were measured in the temperature range from 150 to 220 °C. We have found that the storage and loss shear moduli, G′ and G″, of PVC8 and PVC6 exhibited the power-law dependence on the angular frequency ω at 190 and 210 °C, respectively. Correspondingly, the tan δ values did not depend on ω. These temperatures indicate the critical gel temperature T _gel of each system. The critical relaxation exponent n obtained from these data was 0.75 irrespective of PVC content, which was in agreement with the n values reported previously for the low PVC concentration samples. These results suggest that the PVC gels of different plasticizer content have a similar fractal structure. Below T _gel, the gradual melting of the PVC crystallites takes place with elevating temperature, and above T _gel, a densely connected network throughout the whole system disappears. Correspondingly, the elongational viscosity behavior of PVC8 and PVC6 exhibited strong strain hardening below T _gel, although it did not show any strain hardening above T _gel. These changes in rheological behavior are attributed to the gradual melting of the PVC crystallites worked as the cross-linking domains in this physical gel, thereby inapplicability of the of time–temperature superposition for PVC/plasticizer systems.     

Relationship between rheological and electrical percolation in a polymer nanocomposite with semiconductor inclusions

Microstructure, electrical conductivity, and rheological properties of nanocomposites based on isotactic polypropylene (iPP) containing semiconductor nanoparticles of TiO₂ were studied. Compatibilized and uncompatibilized nanocomposites containing a wide range of TiO₂ concentrations (up to 15 vol%) were prepared by melt compounding in a twin-screw extruder via a masterbatch method. An anhydride-modified PP (AMPP) was used as the compatibilizer. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and image analysis techniques were utilized to study the morphology evolution in the samples. Analyzing the results of direct current (DC) electrical conductivity measurements showed a lower percolation threshold for the uncompatibilized samples, compared to the compatibilized ones. In order to estimate the percolation threshold, linear and nonlinear melt-state viscoelastic properties of the samples were studied. Liquid-solid transition and nonterminal behavior of the uncompatibilized samples were observed at relatively lower range of TiO₂ loading, compared to the compatibilized samples. It was an indication of lower rheological percolation threshold in the uncompatibilized nanocomposites which was in agreement with the electrical percolation threshold. Scaling analysis of strain sweep tests above the percolation thresholds of the nanocomposites resulted in a lower fractal dimension for the uncompatibilized samples.     

Effect of surfactant concentration on the formation and viscoelasticity of anionic wormlike micelle by the methods of rheology and freeze-fracture TEM

Wormlike micelles and network structures were obtained for the samples with the anionic surfactant, sodium dodecyl trioxyethylene sulfate (SDES), and multivalent counterion electrolyte AlCl₃ fixed in a proper concentration according to rheological measurements and the technique of freeze-fracture transmission electron microscopy (FF-TEM). The characteristics of a non-Newtonian fluid and the phenomenon of shear-induced structures transition were acquired from the steady-shear experiments. The TEM micrographs show the coexistence of wormlike micelles, entangled network structures, rod- and sphere- like micelles in the solutions. The Cole-Cole plot shows the rheological behavior of the non-linear viscoelasticity, the departure from the Maxwell model, and a relaxation time that is not simple. The plateau modulus G₀ and the relaxation time F were also investigated to express the rheological properties of the wormlike micellar solutions.     

Dynamic rheological behavior of DBS-induced poly(propylene glycol) physical gels

Physical gelation can be induced in various organic and silicone-based liquids, as well as in polymeric melts, upon addition of 1,3:2,4-dibenzylidene sorbitol (DBS). Such gels are stabilized by the formation of a percolated DBS network composed of highly interconnected nanofibrils. In this study, we explore several factors affecting the rheological properties of poly(propylene glycol) (PPG) gelled by DBS. To ascertain the effect of PPG molecular weight (M_PPG) on gel formation and rheology, we have investigated three series of DBS-induced PPG gels in which M_PPG varies from 425 g/mol to 4000 g/mol. Dynamic stress measurements reveal that the DBS concentration identifying the onset of PPG gelation decreases with increasing M_PPG. Since the solubility parameter (δ_s) of PPG decreases sharply as M_PPG increases over this M_PPG range, this observation suggests that DBS gelation is sensitive to δ_s of the matrix liquid, in agreement with previously reported data collected from DBS-gelled solvents. Moreover, the elastic modulus and yield stress are found to increase with increasing (i) DBS concentration for the three series of PPG/DBS gels examined here and (ii) recovery time after cessation of an introductory shear. Received: 22 February 2000 Accepted: 9 August 2000     

Finite shear strain behavior of a crosslinking polydimethylsiloxane near its gel point

A power law distribution of relaxation times, large normal stress differences, and physical rupture of molecular network strands dominate the shear behavior of polymers at the gel point (critical gels). This is shown in a series of well-defined experiments with increasing magnitude of shear on a model-network polymer system consisting of a linear, telechelic, vinyl-terminated poly-dimethylsiloxane (PDMS) and a four-functional siloxane crosslinker. Stable samples were prepared by stopping the crosslinking reaction at different extents of reaction in the vicinity of the gel point (GP). The Gel Equation has been shown to be valid up to strains of about 2 when using a finite strain tensor. Larger strains have been found to disrupt the network structure of the crosslinking polymer, and introduce a mechanical delay to the gel point. A sample that was crosslinked beyond the gel point (p>p _c ) can be reduced from the solid state to a critical gel, or even to a viscoelastic liquid, depending on the magnitude of shear strain. As a consequence, the relaxation exponent of a critical gel created under the influence of shear is less than that of a quiescently crosslinked critical gel.     

Real-Time Stress Measurement in SiO<Subscript>2</Subscript> Thin Films during Electrochemical Lithiation/Delithiation Cycling

Oxide coatings have been shown to improve the cyclic performance of high-energy density electrode materials such as Si. However, no study exists on the mechanical characterization of these oxide coatings. Here, thin film SiO₂ electrodes are cycled under galvanostatic conditions (at C/9 rate) in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1 M LiPF₆ in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Stress evolution in the SiO₂ thin film electrodes during electrochemical lithiation/delithiation is measured in situ by monitoring the substrate curvature using a multi-beam optical sensing method. Upon lithiation SiO₂ undergoes extensive inelastic deformation, with a peak compressive stress of 3.1 GPa, and upon delithiation the stress became tensile with a peak stress of 0.7 GPa. A simple plane strain finite element model of Si nanotube coated with SiO₂ shell was developed to understand the mechanical response of the core-shell type microstructures under electrochemical cycling; measured stress response was used in the model to represent SiO₂ constitutive behavior while Si was treated as an elastic-plastic material with concentration dependent mechanical properties obtained from the literature. The results reported here provide insights and quantitative understanding as to why the highly brittle SiO₂ coatings are able to sustain significant volume expansion (300%) of Si core without fracture and enhance cyclic performance of Si reported in the literature. Also, the basic mechanical properties presented here are necessary first step for future design and development of durable Si/SiO₂ core shell structures or SiO₂-based electrodes.     

Studies in the rheology of clay-water systems

Summary The rheological properties of sodium Attapulgite sols and gels have been studied as a function of clay concentration, etc.; and the effects of peptising and coagulating electrolytes on these properties have been investigated. These systems show similar properties to those of mixed calcium-sodium Montmorillonite (and Hectorite) clays of equivalent exchangeable sodium content. The intrinsic viscosity and viscosities of the heterocoagulated sols are low, despite the high anisometry of the individual Attapulgite laths (or needles), since disaggregation is incomplete: these sols set to gels of moderate strength. Heterocoagulation is eliminated (as in other clays) by adsorption of peptisors (polyphosphates, etc.) onto the positively charged edges of the dispersed clay particles.Coagulation of the sols dispersed in sodium carbonate solution by electrolytes leads to the formation of highly dissymmetric structures with high viscosity and yield stress. The peptised sols are more stable to electrolyte; and when coagulated, the particle-particle aggregation and structure formation is very much reduced.The previous paper (4) in Soil Science (1957) will henceforth be considered as Part 4 of this series.     

Nonlinear rheological properties and stability of dibenzylidene sorbitol fiber networks in poly(propylene oxide)

Dibenzylidene sorbitol (DBS) is known to gel organic liquids and polymers such as poly(propylene oxide) (PPO) by forming long fibers and fiber networks. Potential applications of these networks depend on their ability to withstand large deformations without significant morphological changes. Therefore, we studied the nonlinear rheological properties of the DBS fiber network in PPO for different DBS concentrations. We found that the concentration dependence of critical deformation (transition from linear to nonlinear viscoelastic region) and gel strength (G′ plateau in the linear region) can be explained on the basis of a model for densely cross-linked fiber gels (MacKintosh et al., Phys Rev Lett 75:4425–4428, 1995). Performing periodic strain sweeps, we found that the decrease in gel strength during the deformation cycles can be ascribed to reversible fiber coarsening. Additionally, start-up experiments showed a strong shear thinning behavior, which is in quantitative agreement with the SGM model (Sollich, Phys Rev E 58:738–759, 1998).     

Synthesis of potassium sodium niobate powders using an EDTA/citrate complexing sol–gel method

Potassium sodium niobate (KNN) powders were synthesized by a modified sol–gel method, using as starting chemicals potassium carbonate, sodium carbonate, and niobium hydroxide, and, as esterification and chelating agents, respectively, ethylene glycol (EG) and ethylene diamine tetraacetic acid (EDTA)/citrate. The effects of citric acid (CA), EG, and EDTA on the stability of the precursor sol were systemically investigated. The powders and gels were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis-differential scanning calorimetry (TGA-DSC). The results indicated that a stable precursor sol was formed when n(CA):n(Mⁿ⁺) = 3:1, n(EDTA):n(NH₄OH) = 1:3.5, and n(CA):n(EG) = 1:2. The xerogel was calcined at 500–950 °C to prepare the KNN powder. Pure KNN perovskite phase with a cube-like structure was synthesized at 850 °C from the precursor sol for a K/Na molar ratio of 1.2. The formation mechanism of the KNN perovskite phase was also discussed.     

Twist viscosity of mixtures of low molar mass nematics

Measurements of the twist viscosity, γ₁(DLS) and twist elastic coefficient, K₂₂(DLS) by electric-field-dependent dynamic light scattering (EFDLS) are reported for low molar mass nematics (LMMNs) 4′-heptyl-4-cyanobiphenyl (7CB) and 4′-octyl-4-cyanobiphenyl (8CB), and their binary mixtures at several temperatures in the nematic state. The results are compared with values (γ₁(Rheol)=α₃–α₂) computed from rheological measurements of the Leslie viscosities α₂ and α₃. For the binary mixtures, at each temperature, the measured twist viscosity γ₁(DLS) and corresponding twist elastic constant K₂₂(DLS) show approximately a linear additive dependence on concentration. The calculated twist viscosity, γ₁(Rheol), agrees with γ₁(DLS) for the pure components, but is significantly smaller for the binary mixtures. Our observations appear to be consistent with a recent report of a discrepancy between values of the tumbling parameter λ, determined using a small-strain oscillatory optical technique, vs those measured by a rheological method. These results suggest that, in the rheological measurements at large strains, the rate of director rotation for mixtures may be affected by a flow-induced change in structure, e.g., shear-induced biaxiality. Received: 17 March 2000 Accepted: 17 July 2000     

Some rheological properties of sodium carboxymethylcellulose solutions and gels

Summary Sodium carboxymethylcellulose (CMC) is a valuable and widely used component of food systems. The rheological properties of a series of CMC solutions and gels have been determined under both steady and imposed sinusoidal shear conditions, over a wide range of shear rates and frequencies, using theWeissenberg Rheogoniometer. Depending upon the CMC type, degree of substitution, and method of solution preparation, the rheological behavior ranged from viscolastic solutions to unctuous gels. If certain polyvalent cations, e.g., Al³⁺, are present, rigid elastic gels may be formed.These results are interpreted in terms of fringe micelles, arising from crystalline residues in the CMC. Gels which show unctuous behavior may be described in terms of a modifiedBingham Body model. Where appropriate, the experimental results are quantitatively analyzed in terms of the parameters of this model. The application of these findings to the use of CMC in food systems is discussed.Hercules Research Center Contribution No. 1600With 7 figures and 1 table     

Thermoreversible gels in oil/EVA systems

In this work we investigate the gel formation of EVA/recycled motor oil systems as a route to obtain synthetic binders which could be used instead of natural bitumen, as well as mixed with natural bitumen to modify adequately its viscoelastic response. The EVA copolymer studied in this work has a vinyl acetate content of 18 wt% and solutions of EVA/motor oil have been prepared up to a concentration of 50 wt%. Dynamic viscoelastic frequency sweeps between 10⁻² Hz and 10² Hz have shown that above 3 wt%, at 25 °C, EVA/motor oil systems form gels. It has been possible to define an elastic equilibrium modulus, G_e, for each gel. The dependence of G_e on concentration has been compared with that of PVC/DOP and SBS/oil gels on the basis of the De Gennes model. Thermal stability of EVA/motor oil gels has also been analyzed, indicating that for the highest polymer concentrations gel point is above 80 °C. Received: 23 December 1999 Accepted: 13 June 2000     

Rheometrical and molecular dynamics simulation studies of incipient clot formation in fibrin-thrombin gels: An activation limited aggregation approach

A rheometrical investigation of incipient clots formed in fibrin-thrombin gels is reported in which the Gel Point (GP) is characterised by frequency independence of the loss tangent in small amplitude oscillatory shear measurements over a wide range of thrombin concentration. Values of the fractal dimension (D_f) of the GP network calculated from measurements are consistent with those reported in simulations of diffusion limited cluster-cluster aggregation (DLCCA) and reaction limited cluster-cluster aggregation (RLCCA), but differ insofar as the values of D_f calculated from the present experiments increase progressively with a reduction in gel formation time. A molecular dynamics simulation (MDS) of systems of rod-like particles was designed to (i) test the hypothesis that the presence of an activation profile in a cluster aggregation model could account for the trend of D_f as a function of gel formation time observed experimentally in fibrin-thrombin gels and whole heparinised blood without recourse to the inclusion of fibrinogen-specific interactions; and (ii) to explore the effect of monomer activation kinetics on the microstructure of fractal clusters formed in systems of rigid rod-like particles. The results identify two possible mechanisms for the increase in D_f as the gel formation time decreases, both being a consequence of altering the evolution of the clustering dynamics by a process referred to herein as activation limited aggregation (ALA). This ALA-based MDS substantiates the experimental findings by confirming the trend evident in the formation of incipient clots in fibrin-thrombin gels and in whole heparinised blood. A mechanism for ALA involving the aggregation of pre-GP sub-clusters is proposed.     

Dependence of linear viscoelastic critical strain and stress values on extent of gelation for a thermally activated gelling system

A large body of literature is focused on the accurate determination of a gel point for systems undergoing a sol-gel phase transition. Investigation into the limiting strain and stress for linear viscoelastic behaviour at various stages of a phase transition such as gelation is a subject that is rarely commented on. The small amplitude oscillatory rheological behaviour of a biopolymer cross-linker system through a thermally activated sol-gel transition is presented. Mechanical spectra were interpreted through application of the gelation criteria of Chambon and Winter (Winter and Chambon 1986; Chambon and Winter 1987), where the (so-called gel strength) parameter S, and relaxation exponent, n are obtained. A detailed study of the limit of linear viscoelasticity yields important trends in critical stress (σ°_c) and critical strain (γ°_c) limits highlighting the possible experimental difficulties associated with mechanical measurements obtained in close proximity to the gel point. Received: 17 March 2000 Accepted: 2 October 2000     

Peculiarities of rheological behavior of filled polymer melts in uniaxial stretching

The peculiarities of theological behavior of filled polymer melts in uniaxial extension in a wide range of strain rates (from 2× 10^–5 to 1 × 10^–1 s^–1) have been studied. Linear polyethylene and 1,4-polybutadiene containing up to 21.5 vol.% of carbon black, silica, calcium carbonate or glass fibers were used. It has been found that the transition from uniform to nonunion stretching due to the neck formation is typical of all specimen compositions, when they approach steady-state straining. Depending on the structure and rheological characteristics of the compositions general conditions for this transition have been established. The general regularities for varying the rheological characteristics of filled polymers in the course of their uniform stretching have been recognized. These regularities depend on the molecular characteristics of the polymer matrix and the presence in the compositions of the structural framework of high disperse filler or the network formed by the entangled fibers. Using polyethylene compositions it has been shown that the introduction of small amounts of disperse or fibrous fillers can give rise to acceleration of the relaxation process in filled polymers.