Permeability of heterogeneous gels

Gels made by radical copolymerization of monofunctional and difunctional monomer units in the presence of swelling medium will tend to be heterogeneous. A case in point is acrylamide co-polymerized with N,N′-methylene bis-acrylamide in water. Such gels can be assumed to be two-phasic with both phases gels, but of different average concentration and average degree of cross-linking. As Weiss and Silberberg have shown, permeability can be used to characterize the distribution in space. In this paper, their earlier model is expanded and improved by considering specifically the permeability of each of the two phases and taking into account that each of these phases separately must have come into swelling equilibrium with the swelling medium, water. It can be shown that only the length of the Kuhn statistical element remains as a free parameter in this model. Essentially the same value of this parameter, however, accurately accounts for the measured permeability. It is found that at an overall volume fraction of about 0.16, the two-phase structure tends to disappear. For higher degrees of crosslinking, this occurs because the more dilute phase takes over the entire space; for more lightly crosslinked systems, the more concentrated phase takes over. The heterogeneity of the distribution lies in the nanometer range and reasonable agreement between the results obtainable from permeability and from viscoelasticity can be demonstrated. These results are consistent with the model for the polymerization process.     

Shear-dependent rheological properties of starch/bentonite composite gels

 Rheological properties of starch/bentonite gels (5.3–8.2% solids, 0–100% starch) were investigated at shear rates 0.0083–0.33 s^-1 (Brookfield viscometer). Prior to these measurements the strain introduced during preparation of the gel was kept as low as possible. Under these conditions six different types of structural units could be identified in the gel: bentonite particles associated in a band-type structure; bands coated with starch polymers; bundles of bands interlaced and enveloped by starch polymers (strands); individual bentonite platelets dispersed in a polymer matrix; starch polymer networks; and swollen granules. A power-law model was fitted to the experimental viscosity data: μ_app= Kγ ^n-1 . In all cases n was found to be less than 0.5. Its value decreased with the ability of the structural components to reorient under applied shear. K was found to be proportional to the compaction and/or entanglement of the structural units. These trends in K and n were further confirmed by the index of thixotropy (IT) and complex modulus of shear elasticity (G ^* ) measurements. Received: 12 August 1996 Accepted: 7 January 1997     

Mechanical properties of liquid-filled shellac composite capsules

This paper describes the mechanical properties of thin-walled, liquid-filled composite capsules consisting of calcium pectinate and shellac. In a series of experiments we measured the deformation of these particles in a spinning drop apparatus. For different pH-values we studied the elastic properties of these particles and compared the obtained results with the mechanical response measured by squeezing capsule experiments. In analogy to these experiments, we also investigated liquid-filled unloaded calcium pectinate capsules without the addition of shellac. The deformation properties of these experiments and the surface Young moduli were in good agreement. Furthermore we investigated the liquid-filled calcium pectinate and the composite capsules by NMR microscopy. These experiments allowed investigations of the membrane thickness and the kinetics of membrane growing. Additional characterizations by stress controlled small amplitude surface shear experiments of similar composed gel layers provided coherent results for the surface Young modulus.     

Mechanical properties of composite polymer microstructures fabricated by interference lithography

We demonstrate that organized, porous, polymer microstructures with continuous open nanoscale pores and a sub-micron spacing obtained via interference lithography can be successfully utilized in a non-traditional field of ordered polymer microcomposites. The examples presented here include porous matrices for the fabrication of binary, glassy-rubbery microcomposites with intriguing mechanical properties with large energy dissipation and lattice-controlled fracturing.     

Mechanical properties of polyimide/multi-walled carbon nanotube composite fibers

A series of polyimide (PI)/multi-walled carbon nanotube (MWCNT) composite fibers were prepared by copolymerizing a mixture of monomers and carboxylic-functionalized MWCNTs, followed by dry-jet wet spinning, thermal imidization, and hot-drawing process. The content of the carboxylic groups of MWCNTs significantly increased when treated with mixed acid, whereas their length decreased with treatment time. Both the carboxylic content and length of MWCNTs influenced the mechanical properties of the composite fibers. Fiber added with 0.1 wt% MWCNTs treated for 4 h exhibited the best mechanical properties, i.e., 1.4 GPa tensile strength and 14.30% elongation at break, which were 51% and 32% higher than those of pure PI fibers, respectively. These results indicated that a suitable MWCNT content strengthened and toughened the resultant PI composite fibers, simultaneously. Moreover, raising draw ratio resulted in the increase of tensile strength and tensile modulus of the composite fibers.     

Scattering properties of agarose gels

Static light scattering and small angle neutron scattering measurements are reported for agarose hydrogels prepared under various conditions of concentration and temperature. For the wide range of transfer wave vector explored, these measurements show that the gels do not display fractal behaviour. Their structure is better described by a stretched exponential form, in which the value of the exponent is n = 0.2. As found by other authors, a maximum in the scattering intensity is observed in the light scattering spectra. The position of the maximum, q_max, depends on the concentration and on the thermal history of the sample. The inverse length 1/q_max is in good agreement with published measurements of the pore size D in this system. Preliminary measurements by small angle scattering indicate that the sol-gel transition is not of spinodal type.     

Viscoelastic properties of ϰ-carrageenan gels

Summary A study has been made of the creep behaviour of -carrageenan in the region of linear viscoelasticity in the temperature interval 9–50 °°C and concentration range 1.0–2.5%. It is shown that the rate of the elementary relaxation processes is independent of the concentration of -carrageenan. The following three temperature intervals where -carrageenan gels exist have been established: (1) the temperature interval corresponding to the stable helix conformation of the macromolecules; (2) the temperature interval of macromoleculer unwinding; (3) the high-temperature interval where the gel three-dimensional network is formed by the unwound macromolecules. The break-down enthalpy of the gel junction zones is 36, 234 and 36 KJ/mole, respectively.     

Supermolecular morphology of thermoreversible gels formed from homogeneous and heterogeneous solutions

The supermolecular structures of thermoreversible gels formed from either homogeneous or heterogeneous solutions were examined by scanning electron microscopy. The morphologies of gels of polyethylene and polystyrene of various tacticities were then related to the phase diagram of the polymer–solvent system. We confirmed the morphological findings of Aubert on isotactic polystyrene gels formed either above the binodal or inside the spinodal and extended his study to gels prepared within the metastable region of the phase diagram. For polystyrenes and polyethylene, the morphology of the gels formed inside the coexistence curve differs markedly from that of gels formed outside. Inside the binodal, gels of polyethylene and polystyrenes exhibit remarkable morphological similarities, indicating a common gelation mechanism, namely, liquid-liquid phase separation. Depending on the concentration, these gels exhibit either an open strut-like network structure or smooth spherical globules. The former is attributed to gelation inside the spinodal whereas the latter is believed to result from gelation in the metastable region. For crystalline polymers, gels formed inside the coexistence curve subsequently undergo crystallization within their polymer-rich phase. The morphology of isotactic polystyrene and polyethylene gels formed outside the binodal consists of overlapping lamellar structures, whereas that of atactic and epimerized polystyrene gels is characterized by a sheet-like structure, differentiating the crystallization-based mechanism from others. © 1993 John Wiley & Sons, Inc.     

Rheological properties of protein-surfactant based gels

Water-based protein-surfactant gels, formed by mixing bovine serum albumin (BSA) and sodium dodecyl sulfate in water, were investigated by rheological methods. The measurements were performed for many different protein-to-surfactant ratios as a function of the applied frequency, stress, or strain, as well as by changing the temperature, in the range between 15 and 65 degrees C. The rheological behavior of the gels as a function of applied frequency is interpreted in terms of the overlapping of at least two viscoelastic relaxation processes. The rheological results indicate the presence of thermal transitions from essentially viscous to mainly elastic regimes, in analogy with the thermal gelation processes observed in polymer solutions. The thermal gelation threshold in the present system is modulated by the protein/surfactant ratio. Differential scanning calorimetry measurements were also performed to determine whether thermal gelation is somehow concomitant to protein denaturation. The results indicate that the thermal denaturation of BSA in protein-surfactant based gels occurs at slightly higher temperatures than in the bulk. Scanning electron microscopy indicates the occurrence in the gel structure of globules formed by the arrangement of fibrils.     

Mechanical and dielectric studies of carrageenan sols and gels

The temperature dependence of the dynamic shear modulus, strain optical coefficient, DC conductivity, and complex dielectric spectrum of κ- and ι-carrageenan aqueous solutions with K, Ca, Cs, and Na were measured in order to clarify the formation process of the cross-linking region and the gel network structure. From the correlation analysis between the shear modulus and the strain optical coefficient, we found that the stress inducing unit orientation increases with decreasing temperature, which strongly suggests that the branching number in a cross-linking region increases with decreasing temperature, which depends on counterion species. In terms of the correlation parameters, an increasing scheme of the branching number depends on counterion species. Just below the coil-helix transition temperature, dielectric relaxation arises, with relaxation time ∼100μs and relaxation strength ∼10³. Dielectric relaxation can be assigned to the counterion fluctuation in the parallel direction to the helical axis. The fluctuation distance of the counterion estimated from the relaxation time increases sharply in the initial stage of gelation and gradually reaches a constant value. We concluded that the longitudinal length of the aggregated region increases sharply at the initial state of gelation while the number of helical molecules bundled in a cross-linking region increases successively with decreasing temperature.     

Mechanical properties and morphological structures of short glass fiber reinforced PP/EPDM composite

The mechanical properties and crystal morphological structures of short glass fiber (SGF) reinforced dynamically photo-irradiated polypropylene (PP)/ethylene-propylene-diene terpolymer (EPDM) composites were studied by mechanical tests, wide-angle X-ray diffraction (WAXD), optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analyzer (TGA). The mechanical properties of PP/EPDM composites, especially the tensile strength were greatly strengthened by dynamically photo-irradiation and the incorporation of SGF. The results from the WAXD, SEM, DSC, and TGA measurements reveal: (i) the formation of β-type crystal of PP in the PP/EPDM/SGF composite; (ii) the fiber length in dynamically photo-irradiated PP/EPDM/SGF composites are general longer than that in corresponding unirradiated samples. The size of EPDM phase in the photo-irradiated composites reduces obviously whereas the droplet number increases; (iii) photo-irradiation improves the interface adhesion between SGF and polymer matrix; (iv) the melting and crystallization temperatures of the photo-irradiated composites are not affected greatly by increasing the SGF content; (v) the thermal analysis results show that the incorporation of SGF into PP/EPDM plays an important role for increasing its thermal stability.     

Optimization of asymmetric permeation in heterogeneous composite membranes

Asymmetric permeation in two-phase composite membranes with heterogeneous structures represented by a one-dimensional distribution of composition is treated theoretically on the basis of an irreversible thermodynamic transport equation. It is assumed that the permeability of one of the component phases is a monotone function of the activity of permeant while that of the other phase is constant, and that the permeability of the composite membrane is given by the volume average of the resistance coefficient, which is the inverse of permeability. Under these assumptions, it is shown that the optimal membrane which maximizes the degree of asymmetric permeation reduces to a binary laminate membrane. The condition for constructing the optimal laminate membrane is obtained explicitly. Conversely a condition on a desirable membrane component which realizes an arbitrary degree of asymmetric permeation is presented. These results can be applied to the optimal design of a membrane valve which is a chemical analog of a diode. © 1993 John Wiley & Sons, Inc.     

Elasticity and flow properties of actin gels

Actin gels formed by polymerizing monomeric actin have been studied by use of small amplitude oscillatory deformations and steady shear flow. The length of actin filaments within the gel was varied by copolymerization in the presence of the filament-capping protein gelsolin. The results for short filaments are in qualitative agreement with a model for semi-dilute solutions of inter-penetrating rods. Long filaments give rise to additional motions, believed to be flexing of rods. Steady shear viscosities, at high shear rates, are independent of initial filament length. Results are explained as due to breaking of filaments in shear flows.     

Mechanical behaviour of nano composite aerogels

In order to improve the mechanical properties of silica aerogels, we propose the synthesis of nano composite aerogels. Silica particles (20–100 nm) are added in the monomer solution, just before gelling and supercritical drying. The silica particles addition increases the mechanical properties, but also affects the aggregation process, the aerogel structure and the pore sizes. We discuss the different parameters which infer in the mechanical behaviour of silica aerogel such as: brittle behaviour, load bearing fraction of solid (pore volume), internal stresses (shrinkage), size and distribution of flaws, subcritical flaws propagation (chemical susceptibility). With silica particles addition, the mechanical properties rapidly increase, stiffening and strengthening the structure by a factor 4–8. Moreover, the mechanical strength distribution and the Weibull modulus characterizing the statistical nature of flaws size in brittle materials show a more homogeneous strength distribution. The composite structure is made of two imbricate networks, the polymeric silica and the particles silica networks. Ultra Small Angle X-ray Scattering experiments show that besides the fractal network usually built up by the organosiloxane, the silica particles is forming another fractal structure at a higher scale. The fractal structure could be related to the low Weibull parameter characteristic of a large flaws size distribution, pores being the critical flaws.     

Mechanical properties of interlayer hybrid textile composite materials based on modified aramid and UHMWPE fabrics

Aramid fibers and ultra-high molecular weight polyethylene (UHMWPE) fibers lack active surface functional groups, and the surface is smooth, limiting their practical application in textile composite materials. In this study, zinc oxide nanorods were used to grow on aramid fibers surfaces, and oxygen plasma followed by treatment with a silane coupling agent was used to modify UHMWPE fibers. The effects of surface modification on the surface morphology and composition, and mechanical properties of fibers and composites were investigated. The mechanical response of interlayer hybrid textile composite materials based on modified aramid and UHMWPE fabrics was examined. The results reveal that surface roughness, active surface functional groups, and wettability that can be controlled by treatment conditions and parameters are important for improving interface adhesion. In addition, the interlayer hybridization pattern as a result of using dissimilar layer materials and altering stacking sequence has a great impact on the mechanical behavior of hybrid textile composite materials.     

Gelatine/silicate interactions: from nanoparticles to composite gels

The possibility to design new composites associating biopolymers with mineral phases relies on the understanding and control of their mutual interactions. In this work, aqueous solutions of gelatine and sodium silicate were mixed at pH 5, 37 degrees C and left to stand at 20 degrees C for 1 day. At low gelatine and high silicate contents, precipitates were obtained, containing a fixed silicon/polymer molar ratio. Scanning electron microscopy (SEM) reveals that they are formed of large aggregates of platelets, constituted of closely-packed nanoparticles. For high gelatine contents, composite gels were formed consisting of silica particles dispersed in the biopolymer matrix. Swelling studies indicate that the addition of silica decreases the stability of the gels by inducing gelatine depletion in solution. Similar experiments conducted at pH 7 show that at this pH, silicates are more effective at precipitating gelatine. A model is proposed for the formation of the composites, based on the electrostatic interactions arising between silicates and polymer chains. These results are discussed in the context of hybrid biomaterials design and biosilicification processes.     

Dynamic scaling properties of TeO2-based gels

Homogeneous, transparent, and mechanically rigid gels have been successfully synthesized in the tellurium isopropoxide-isopropanol-citric acid and water system. The sol to gel transition and the gels microstructure have been studied by using small angle X-ray scattering (SAXS) experiments. For any value of the two key synthesis parameters, which are the citric acid ratio and the alkoxide concentration, very small Te-rich elementary particles, about 1-1.5 nm in radius, form immediately when the water is added, leading to colloidal sols. During gelation, these elementary particles stick progressively together to build up fractal aggregates by a pure hierarchical aggregation process which has been identified as a reaction-limited cluster aggregation (RLCA) mechanism. The SAXS curve analysis, based on scaling concepts, shows that the gelling network exhibits a time and length scale invariant structure factor characterized by self-similarity. This self-similarity is also displayed for a wide range of chemical compositions and the gel microstructures only differ in their fractal aggregate size according to the tellurium isopropoxide concentration as well as the citric acid ratio.     

Synthesis and some properties of titanium-containing silica gels

Microporous silica gels containing small amounts of titanium ions have been synthesized. Porous structure and surface active sites of silica gels have been studied. It has been found that the titanium ions are distributed uniformly in silica gel matrix, substituting silicon ions isomorphically.     

Waterborne polyurethane-coated polyamide/fullerene composite films: Mechanical,thermal, and flammability properties

Novel waterborne polyurethane (WPU) was prepared and coated on nylon 12 (Ny12) and fullerene-C60 (Full-C60, 1–10 wt%) composite films using simple dip coating technique. In Ny12/Full-C60 composite, fullerene nanoparticles were dispersed in a wavy layered pattern, whereas coated WPU/Ny12/Full-C60 films depicted uniform pattern of non-overlapping scales. WPU/Ny12/Full-C60 1–10 showed higher values of tensile strength and modulus, 91.4–98.1 MPa and 52.2–57.9 GPa, respectively. In WPU/Ny12/Full-C60 1–10, maximum degradation temperature was increased to 598°C and char yield to 35%. Increasing fullerene content from 1 to 10 wt% decreased maximum peak heat release rate from 209 to 132 kW m^?2, i.e., 53% reduction in flammability compared to WPU.