Electrokinetic Properties of Acid-Activated Montmorillonite Dispersions

In this study, the influence of pH, electrolyte concentration, and type of ionic species on the electrokinetic properties (zeta potential and electrokinetic charge density) of the acid-activated montmorillonite mineral have been investigated using the microelectrophoresis method. The electrokinetic properties of acid-activated montmorillonite dispersions have been determined in aqueous solutions of mono-, di-, and trivalent salts and divalent heavy metal salts. Zeta potential experiments have been performed to determine the point of zero charge (pzc) and potential determining ions (pdi). The zeta potential values of the acid-activated montmorillonite particles were negative and did not vary significantly within the pH range studied. Acid-activated montmorillonite dispersions do not have point of zero charge (pzc). The valence of the electrolytes has a great influence on the electrokinetic behavior of the suspension. A gradual decrease in the zeta potential (from ?25 mV to ?5 mV) occurs with the monovalent electrolytes when concentration increased. Divalent and heavy metal electrolytes have less negative z-potentials due to the higher valence of ions. A sign reversal of z-potential has been observed at AlCl₃, FeCl₃, and CrCl₃ electrolytes (potential determining ions) and zeta potential values have had a positive sign at high electrolyte concentrations.

The electrokinetic charge density of acid-activated montmorillonite has shown similar trends for variation in mono- and divalent electrolyte solutions. Up to concentrations of ca. 10^?3 M, it has remained practically constant at approximately 0.5 × 10^?3 C m^?2 For higher concentrations of monovalent electrolytes more negative values (?16 × 10^?3 C m^?2) were observed. It has less negative values in divalent electrolyte concentrations according to monovalent electrolytes (?5 × 10^?3 C m^?2). For low concentrations of trivalent electrolytes, the electrokinetic charge density of montmorillonite particles is constant, but at certain concentrations it rapidly increased and changed its sign to positive.     

Preparation and properties of organosoluble montmorillonite/polyimide hybrid materials

Organosoluble montmorillonite/polyimide hybrids were prepared using a monomer solution intercalation polymerization method. Montmorillonite was organo-treated with p-aminobenzoic acid and the organosoluble polyimide was based on pyromellitic dianhydride and 4,4′-diamino-3,3′-dimethyldiphenylmethane. The particle size of montmorillonite in the hybrid containing 1 wt % of montmorillonite is about 400 nm. The strength and the toughness of montmorillonite/polyimide hybrids are improved simultaneously when the montmorillonite content is below 5 wt %. The thermal stabilities of montmorillonite/polyimide hybrids are obviously improved and their thermal expansion coefficients are reduced. When the montmorillonite content is below 5 wt %, the montmorillonite/polyimide hybrids are soluble in strong aprotonic polar organic solvents. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2063–2068, 1999     

Preparation and characterization of PVA/OMMT composites

In this study, polyvinyl alcohol/organically modified montmorillonite (HDA/MMT; organoclay) composite was prepared for the intercalation processes. Firstly, the rheological behavior of aqueous montmorillonite dispersions was investigated as a function of solid content. Hexadecylamine (HDA) was added to the montmorillonite dispersion (2%, w/w) in different concentrations in the range of 5 × 10^?4 – 9 × 10^?3 mmol/L. The basal spacing of the organoclay (OMMT) was studied by X‐ray diffraction. The FTIR spectra are obtained from the modified montmorillonite products, which revealed the characteristic absorbencies after treatment with HDA. HDA/MMT/PVA composite, which was produced by the reaction of 1 wt % PVA solution with organoclay complex, is characterized by the rheology, electrokinetic, XRD, FTIR, and SEM techniques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:2315–2323, 2006     

The effect of polyurethane on NaMt and ONaMt dispersions

The rheological parameters of clay suspensions can be used to examine particle–particle interactions. The polymers that have been added to the clay suspensions interact with clay particles, according to their ionic or non-ionic character. In this study, we have synthesized an organoclay (ONaMt) form of a Na-activated montmorillonite (NaMt) and investigated rheological and electrokinetic properties of their water based dispersions. After that, the medium is changed with water based solution of PU and the changes on the rheological and electrokinetic properties and the structural analysis of the materials were studied. All the results have been commented by taking the interaction between the clay and the polymer molecules into consideration. X-ray diffraction (XRD) studies showed that basal spacing of NaMt samples are more expandable, up to 22 Å, than ONaMt samples, which their expendabilities are relatively constant at about 19 Å.     

Rheological,electrokinetic, and morphological characterization of alginate–bentonite biocomposites

We prepared biocomposite gel dispersions involving sodium alginate (Na‐Alg) and calcium bentonite (Ca‐B) with various solid concentrations and characterized their rheological, electrokinetic, and morphological properties. The flow properties, such as the apparent and plastic viscosities, shear stress, and yield value point, changed with increasing clay dosage. The viscosities of the homogeneous dispersions were represented by the Herschel–Bulkley model. The ζ‐potential results were examined in the light of different characterization methods (X‐ray diffraction, Fourier transform infrared spectroscopy, and atomic force microscopy) to understand the interactions between the Na and Ca ions of the alginate biopolymer and bentonite clay. A plausible structural model for the alginate–bentonite composite gel, known as the egg‐box model, is proposed. The presence of Ca ions in the Ca‐B partially crosslinked Na‐Alg may be regarded as an excellent example of a self‐assembling process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

The influence of food emulsifiers on fat and sugar dispersions in oils. II. Rheology,colloidal forces

The influence of food emulsifiers on the viscoelastic properties (storage modulus and yield value) of fat and sugar dispersions in vegetable oils has been investigated. It was found that almost all of the emulsifiers tested influence the rheology of the dispersions. The magnitude and the direction of the rheological changes depend on both the type and the amount of emulsifier. In most cases the changes are relatively small, especially for fat crystals. Generally speaking, the largest changes are caused by lecithins and saturated monoglycerides. The magnitudes of colloidal forces and equilibrium distances between the particles have been estimated from the rheological network model of van den Tempel [J. Colloid Sci. 16:284 (1964)] and from the correlation of the yield value to the interaction energy by Gillespie [J. Colloid Sci. 15:219 (1960)] and Tadros [Langmuir 6:28 (1990) andChemistry and Industry 7:210 (1985)]. The results indicate that van der Waals forces alone cannot be responsible for the interparticle interaction in fat or sugar dispersions. The formation of water bridges is discussed as a probable source of interaction in both cases. Furthermore, the validity of the network model for fat and sugar dispersions in oils is questionable.     

Effect of montmorillonite on the rheological properties of dually crosslinked guar gum‐based hydrogels

One strategy to create chemical and physical cross‐links simultaneously is to introduce into the chemical network hydrogen bonding with clay nanofillers. Understanding the relaxation mechanisms of these systems is crucially important and has drawn the extensive interest of many scientists. In this work, the influence of different amounts of montmorillonite on the structural and rheological properties of guar gum hydrogels was investigated. Depending on the clay content, different nanostructures were identified by X‐ray diffraction (XRD) and their effect on the rheological properties of the dual hydrogels was studied. From stress and frequency sweep tests it emerged that all the samples exhibit a weak gel behavior and showed a maximum for G″ that can be ascribed to the breaking and reforming of transient physical crosslinks. This relaxation mode is more pronounced for the hydrogel for which a minimum in the swelling degree was observed. On the basis of these results, a model structure was proposed according to which the clay sheets act as effective multifunctional cross‐linkers. The more homogeneously dispersed are the clay platelets, the higher is the density of physical crosslinks. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41373.     

Mechanical properties and drug release rate of poly(vinyl alcohol)/poly(ethylene glycol)/clay nanocomposite hydrogels: Correlation with structure and physical properties

Poly(vinyl alcohol)/poly(ethylene glycol) hydrogels containing curcumin as a drug and the various amounts of a montmorillonite nanoclay are prepared using the freezing–thawing method. Nanoclay quantity influence on the physicomechanical properties and the drug release rate of the hydrogel as well as relationship between them is investigated. X-Ray diffraction and Atomic force microscopy analysis reveal the nanoclays have an intercalation structure in the hydrogel, and the hydrogel crystallization decreases with increasing the nanoclay inclusion. From the SEM micrographs observation, it was revealed that due to the presence of the nanoclay in the hydrogel, its porosity decreased. The naonoclay has an amount-depended dual effect on the hydrogel swelling. The swelling mechanism is a normal Fickian diffusion for all the hydrogel samples. Strong physical interactions between the nanoclays and the polymer chains in the nanocomposite hydrogels are evidenced by the rheological studies. These interactions lead to significant reinforcement of the hydrogel tensile strength, intensified by the nanoclay amount. Interestingly, the nanoclays show the capability of accelerating and, also, decelerating the drug release of the hydrogel. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47843.     

Rheological behavior of waterborne polyurethane/starch aqueous dispersions during cure

Isothermal rheological behaviors of waterborne polyurethane (WPU)/starch aqueous dispersions during cure were investigated with a small-amplitude oscillatory shear flow experiment to evaluate their crosslinked structure and to predict their mechanical properties, for the first time. An abrupt increase in the elastic storage modulus (G′), the viscous loss modulus (G″), the complex dynamic viscosity (η^*) and the loss tangent (tan δ) was observed during the curing process of the dispersions, as a result of the formation of a fractal polymer gel. The gel point (t_gel) was determined from the intersection in tan δ vs curing time for different constant shear frequencies, where tan δ was frequency independent and all curves crossed over, indicating the validity of the Winter–Chambon criterion for the complex system. The values of the power law exponent (n) and the gel strength (S_g) at the gel point indicated that with an increase of starch content the crosslinked WPU/starch gels underwent a transition from weak fractal to strong elastic ones. Moreover, the WPU/starch composite sheets, obtained from the aqueous dispersions with relatively high S_g values, also exhibited the increased tensile strength (σ_b) and Young's modulus (E). Their structure–mechanical properties relationship and the phase transitions of dispersed starch–dual-phase continuity–starch matrix were revealed. This work confirmed that the rheological characters could be used to predict the mechanical properties of the WPU materials blended with natural polymer.     

Improved mechanical and swelling behavior of the composite hydrogels prepared by ionic monomer and acid-activated Laponite

A composite hydrogel (CH) with much improved mechanical and swelling properties was prepared using an ionic monomer and acid-activated Laponite XLS which was used as a cross-linking agent. Addition of acid-activated clay solved the gelation problem when ionic monomers were added to clay mineral dispersions. Reaction of Laponite XLS with sulfuric acid yielded amorphous silica. A dispersion of the acid-activated Laponite and the monomers was used to synthesize composite hydrogels by in-situ polymerization. The FT-IR spectra and rheological results of the composite hydrogels demonstrated the formation of a network. The equilibrium swelling ratios of composite hydrogels (> 6000 g/g) were more than 18 times larger than traditional organic cross-linked hydrogels. The moduli G′ and G″ in the observed frequency range were about 4 and 10 times larger than those of organic cross-linked hydrogel (OR gel). The improvement in both the equilibrium swelling ratio and mechanical strength was attributed to the homogeneous cross-linked network structure.     

Synthesis and characterization of polyurethane cationomer/MMT hybrid composite

BACKGROUND: The development of polymeric nanocomposites incorporating intercalated or exfoliated layered silicate clays into the organic matrix has been substantially motivated by the significant improvements induced by the presence of the inorganic component. Moreover, understanding and controlling the dispersion of inorganic layers into segmented polyurethane matrices by means of ionic interactions, and exploiting these interactions to enhance physicomechanical behaviour, could be of great interest in the field of polymer nanocomposites. RESULTS: New cationic polyurethane elastomers were prepared starting from poly(butylene adipate)diol (M_n = 1000 g mol^?1), 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol and N‐methyldiethanolamine or N,N′‐β‐hydroxyethylpiperazine, used as potential quaternizable moieties. The characterization of the polymers was achieved using specific analyses employed for the macromolecular samples (Fourier transform infrared and ¹H NMR spectroscopy, thermogravimetric analysis (TGA), gel permeation chromatography). An extension of our research on polymers reinforced with organically modified montmorillonite (OM‐MMT) in order to prepare hybrid composites with improved properties was performed and the resulting materials were characterized using TGA, X‐ray diffraction, atomic force microscopy and scanning electron microscopy. Also, the mechanical properties of the cationic polyurethane/OM‐MMT composites were investigated in comparison with the pristine ionic/non‐ionic polymers and their composites containing non‐ionic polymer blended with OM‐MMT or ionic polymer and unmodified MMT. CONCLUSION: The insertion of the organically modified clay into the polymeric matrix gave an improvement of the mechanical properties of the polyurethane composites, especially the tensile strength and stiffness of the hybrid materials. Copyright © 2009 Society of Chemical Industry     

Rheological study of aqueous dispersions of in situ gelable thermosensitive polymer nanogels

Thermosensitive poly(N‐isopropylacrylamide‐co‐acrylamide) nanogels with varied monomer compositions were prepared by precipitation polymerization. The aqueous dispersions of these thermosensitive nanogels (9 wt% of nanogel particles in phosphate‐buffered saline solution) exhibited in situ gelable characteristics. A steady‐state and dynamic rheological analysis demonstrated that the nanogel dispersions were typical pseudoplastic liquids at room temperature. The viscosity of the nanogel dispersions at a constant shear rate increased with an increase of the acrylamide content. When the temperature was increased to 37°C, the pseudoplastic liquid turned into an elastic solid, as the result of a sol–gel phase transition of the nanogel aqueous dispersion during the raise of the temperature. Dynamic temperature ramp circle curves suggest that the sol–gel transition was reversible but with a clear hysteresis. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Pervaporation Separation of p-/o-Xylene Mixtures Using HTPB-Based Polyurethaneurea Membranes

Hydroxy terminated polybutadiene (HTPB)-based polyurethaneurea membranes with and without cross-linkage were synthesized and first used as membrane material to separate p-/o-xylene mixtures by pervaporation. Compared with HTPB-PU (without cross-linkage) membranes, HTPB-DVB-PU (cross-linked HTPB-PU with divinyl benzene) membranes demonstrated a lower degree of swelling in xylene isomer solutions and noticeable improved separation factor of p-/o-xylene. On the other hand, the amount of p-xylene adsorbed in HTPB-DVB-PU membranes increased significantly rather than that of o-xylene. While the separation factor of p-/o-xylene increased but the total flux decreased with increasing DVB content, which can be ascribed to the improved chemical structure and more homogeneous chain structures of the HTPB-DVB-PU membranes. The p-xylene normalized permeation rate and separation factor of p-/o-xylene of HTPB-DVB-PU membrane reached 2.70 kgµm/m²h and 2.23, respectively, at a feed concentration of 10 wt% p-xylene at 30°C.     

Effect of hydrophilic monomer on the surface properties of cationic polyurethane‐fluorinated acrylate hybrid dispersions

Cationic polyurethane‐fluorinated acrylate hybrid dispersions (PUFA) were prepared by the copolymerization of styrene, butyl acrylate, and 2,2,3,4,4,4‐hexafluorobutyl methacrylate in the medium of crosslinked polyurethane via phase inversion polymerization. The said polyurethane was synthesized in acetone from 2,4‐tolyene diisocyanate, N‐methyldiethanolamine, trimethylolpropane, and soft polyester diol block. The influences of hydrophilic monomer on the surface properties, immersion behaviors, particle size and, zeta potential of the dispersions were investigated. The results show that the addition of hydrophilic monomer can be advantaged to the stability of dispersions and yet will increase the surface free energy by more than 19.9%. The PUFA coating films cured at ambient conditions have the lower surface free energy (less than 0.02033 J/m²). At the same time, there is an obvious mobility of fluorinated groups in fluorinated polymer films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Ultrahigh molecular weight polyethylene/polypropylene/organo‐montmorillonite nanocomposites: Phase morphology,rheological, and mechanical properties

Phase morphology, rheological, and mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE)/PP/organo‐montmorillonite nanocomposites were investigated in this work. The results of TEM and XRD indicated that the organo‐montmorillonite PMM prepared with the complex intercalator [2‐methacryloyloxyethyldodecyldimethylammonium bromide/poly(ethylene glycol)] were exfoliated and dispersed into UHMWPE matrix, and the synergistic effect of the complex intercalator on the exfoliation and intercalation for montmorillonite occurred. Besides, the presence of PMM in UHMWPE matrix was found able to lead to a significant reduction of melt viscosity and enhancement in tensile strength and elongation at break of UHMWPE, except that izod‐notched impact strength was without much obvious change. The dispersed PMM particles exhibited a comparatively large two‐dimensional aspect ratio (L_clay/d_clay = 35.5), which played an important role in determining the enhancement of mechanical properties of UHMWPE nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of particle size and fluid fraction on rheological and extrusion properties of crosslinked hyaluronic acid hydrogel dispersions

Crosslinked hyaluronic acid (HA) hydrogels are widely used in gel/HA fluid formulations as a viscosupplement to treat joint diseases; thus, it is important to characterize these hydrogels in terms of their particle size and to investigate the effects of the gel/fluid mixtures on their rheological properties and extrusion force. Hydrogels previously crosslinked with divinyl sulfone were sheared in an Ultra‐Turrax unit to produce particles with mean diameters ranging from 20 to 200 μm. Hydrogels with 75–100 μm mean diameters were also evaluated in dispersions containing a 20–40% mass fraction of HA fluid. The mean diameters were measured by laser light scattering and the rheological behavior was determined by oscillatory and steady measurements in parallel plate geometry. The HA hydrogels exhibited the typical behavior of so‐called weak gels, as analyzed by the storage and loss moduli G′ and G″, respectively. The viscoelasticity, the viscosity, and the extrusion force increased with the hydrogel particle size. The fluid phase dispersions decreased both moduli. At 40% fluid fraction, the gel characteristics were lost and the dispersion behaved as a fluid. Based on these results, the particle size and HA fluid fraction in hydrogel dispersions may be optimized to develop more efficient viscosupplement formulations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microstructural changes of reference montmorillonites by cationic surfactants

The characteristics of montmorillonites modified with the cationic surfactant hexadecyltrimethylammonium (HDTMA) were evaluated by investigating adsorption isotherms and microstructures. The interlayer structure of montmorillonite intercalated with alkylammonium cations was affected by several factors: the density of the layer charge, degree of exchange, and mutual interaction between alkyl chains. Especially, the surface charge appeared to have an influence on interlayer expansion as a function of surface coverage. Our transmission electron microscopy (TEM) data on the montmorillonite treated with HDTMA revealed that different types of organic derivatives with distinct swelling patterns occurred as a result of the different layer charge densities or distributions on the clay mineral.     

Preparation of adherent films of poly-p-xylylenes on aluminum by electrolysis

The electrolysis of solutions of p-methylbenzyltrimethylammonium nitrate or, better, p-xylylenebis(trimethylammonium nitrate) or p-xylylenebis(triphenylphosphonium chloride or bromide) in a polar organic solvent with an aluminum cathode and a platinum anode results in the formation of adherent coatings of poly-p-xylylene on the cathode. The mechanism of this reaction involves the electrochemical generation of p-xylylene and its subsequent polymerization on the aluminum cathode. Competing reactions are formation of p-xylene and reduction of the solvent.     

Rheological properties of sodium montmorillonite dispersions

The rheological behaviour of dispersions of montmorillonite in water is highly pH- and salt-dependent. This is exemplified for 4% (wt/wt) dispersions of montmorillonite from Wyoming and its homoionic sodium form in water, 0.01 M NaCl and 0.1 M NaCl solutions, at different pH and at temperatures from 20°C to 60°C. Generally, the shear stress (for instance, at shear rates of about 100 s⁻¹) decreases sharply in an acidic medium to a minimum around pH 6 (pH 7.5 for the homoionic sodium form) and then increases again very strongly. Thixotropic and antithixotropic behaviour depend on pH, salt concentration and temperature.The presence of Ca²⁺ ions (molar ratio Na/Ca about 6.5/1) in the “pristine” montmorillonite affects the type of flow very sensitively. Ca²⁺ ions convert diffuse ionic layers into quasicrystalline structures with a central layer of gegen ions. Attractive potentials are then created in the contact regions between the particles, even in diluted salt solutions. Formation of band-like structures (as in the “Bändermodell” of A. Weiss) is promoted.Further, results are reported on the influence of particle size (fractions < 0.06 μm to 2 μm) on the flow behaviour at different concentrations of homoionic sodium montmorillonites from Amory and Cameron.     

Influence of new thermoplastic sizing agents on the mechanical behavior of poly(ether ketone ketone)/carbon fiber composites

In this study, unidirectional poly(ether ether ketone)/carbon fiber (CF) composite sheets were elaborated with unsized, epoxy‐sized, and thermoplastic‐sized CFs by hot‐press molding. The thermoplastic sizings that we used were poly(ether imide) (PEI) and poly(ether ketone ketone) oligomer aqueous dispersions. Scanning electron microscopy observation of the composites freeze fractures showed that unlike unsized or epoxy‐sized CFs, the thermoplastic sizings improved the interaction between the fibers and the matrix. A comparative study of the mechanical relaxations by dynamic mechanical analysis was carried out on the different composites before and after immersion in kerosene. At low temperature, the PEI sizing had a significant influence on the β relaxation, particularly after kerosene immersion. The thermoplastic sizings did not modify the glass‐transition temperature but improved the kerosene resistance on the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42550.