Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Separating viscoelasticity and poroelasticity of gels with different length and time scales

Viscoelasticity and poroelasticity commonly coexist as time-dependent behaviors in polymer gels. Engineering applications often require knowledge of both behaviors separated; however, few methods exist to decouple viscoelastic and poroelastic properties of gels. We propose a method capable of separating viscoelasticity and poroelasticity of gels in various mechanical tests. The viscoelastic characteristic time and the poroelastic diffusivity of a gel define an intrinsic material length scale of the gel. The experimental setup gives a sample length scale, over which the solvent migrates in the gel. By setting the sample length to be much larger or smaller than the material length, the viscoelasticity and poroelasticity of the gel will dominate at different time scales in a test. Therefore, the viscoelastic and poroelastic properties of the gel can be probed separately at different time scales of the test. We further validate the method by finite-element models and stress-relaxation experiments. © 2014 The Chinese Society of Theoretical and Applied Mechanics; Institute of Mechanics, Chinese Academy of Sciences and Springer-Verlag Berlin Heidelberg.

Stretchable liquid-crystal blue-phase gels.

Liquid-crystalline polymers are materials of considerable scientific interest and technological value. An important subset of these materials exhibit rubber-like elasticity, combining the optical properties of liquid crystals with the mechanical properties of rubber. Moreover, they exhibit behaviour not seen in either type of material independently, and many of their properties depend crucially on the particular mesophase employed. Such stretchable liquid-crystalline polymers have previously been demonstrated in the nematic, chiral-nematic, and smectic mesophases. Here, we report the fabrication of a stretchable gel of blue phase I, which forms a self-assembled, three-dimensional photonic crystal that remains electro-optically switchable under a moderate applied voltage, and whose optical properties can be manipulated by an applied strain. We also find that, unlike its undistorted counterpart, a mechanically deformed blue phase exhibits a Pockels electro-optic effect, which sets out new theoretical challenges and possibilities for low-voltage electro-optic devices.

Luminescence properties of sol-gel derived silica gels doped and undoped with RE-complexes (RE=Eu, Tb)

The luminescence properties of silica gels and silica gels doped with two rare earth complexes, Eu(TTA)(3) and Tb(o-CBA)(3) (TTA=thenoyltriffuocetate, o-CBA=o-chlorobenzoic acid) are reported and discussed. Pure silica gels show a blue luminescence, and the maximum excitation and emission wavelengths depend strongly on the solvents used. Both of the studied rare earth complexes exhibit the characteristic emissions of the rare earth ions in silica gels, i.e., Eu3+5D0-->F-7(J)(J=0,1,2,3,4), Tb3+5D4-->F-7(J)(J=3,4,5,6) transitions. Compared with the pure RE-complexes powder, the silica gels doped with RE-complexes show fewer emission lines of the rare earth ions. Furthermore the rare earth ion (Tb3+) presents a longer lifetime (1346 mu s) in silica gel doped with Tb(o-CBA)3 than in pure Tb((o-CBA)(3) powder (744 mu s). The reasons responsible for these results are discussed in the context.

On the evaluation of diffusivities in gels using the diffusion cell technique

Modeling of the gel-immobilized cell system requires accurate measurement of diffusion coefficients. Three methods of the quasi-steady-state (QSS) method, the time-lag (TL) method and a variant quasi-steady-state (VQSS) method were critically assessed and compared for the evaluation of diffusivities using the diffusion cell technique. Experimental data from our laboratory were used for the analysis of the influence of crucial theoretical assumptions not being fulfilled in each method. The results highlighted a risk in obtaining highly variable diffusion coefficients by not validating the QSS and the accuracy of the measurements. In the TL method, the estimation of diffusivities based on the plot intercept that was mostly used in the literature, results in a many fold lower value when compared to that based on the plot slope. The comparison with the QSS and VQSS methods confirmed similar diffusivity obtained by the TL method based on the plot slope. It thus suggested that the correct estimation of diffusivities by the TL method could be based on the plot slope only. Furthermore, the errors associated with the solute mass in the gel, the sample withdrawal and the non-negligible concentration changes in the chambers were also discussed. It is concluded that diffusion cell technique has to be employed cautiously for a correct evaluation of diffusivities. (C) 2001 Elsevier Science B.V. All rights reserved.

Examination of the flow rheological and textural properties of polymer gels composed of poly(methylvinylether-co-maleic anhydride) and poly(vinylpyrrolidone): rheological and mathematical interpretation of textural parameters.

The purpose of this study was to mathematically characterize the effects of defined experimental parameters (probe speed and the ratio of the probe diameter to the diameter of sample container) on the textural/mechanical properties of model gel systems. In addition, this study examined the applicability of dimensional analysis for the rheological interpretation of textural data in terms of shear stress and rate of shear. Aqueous gels (pH 7) were prepared containing 15% w/w poly(methylvinylether-co-maleic anhydride) and poly(vinylpyrrolidone) (PVP) (0, 3, 6, or 9% w/w). Texture profile analysis (TPA) was performed using a Stable Micro Systems texture analyzer (model TA-XT 2; Surrey, UK) in which an analytical probe was twice compressed into each formulation to a defined depth (15 mm) and at defined rates (1, 3, 5, 8, and 10 mm s-1), allowing a delay period (15 s) between the end of the first and beginning of the second compressions. Flow rheograms were performed using a Carri-Med CSL2-100 rheometer (TA Instruments, Surrey, UK) with parallel plate geometry under controlled shearing stresses at 20.0°?±?0.1°C. All formulations exhibited pseudoplastic flow with no thixotropy. Increasing concentrations of PVP significantly increased formulation hardness, compressibility, adhesiveness, and consistency. Increased hardness, compressibility, and consistency were ascribed to enhanced polymeric entanglements, thereby increasing the resistance to deformation. Increasing probe speed increased formulation hardness in a linear manner, because of the effects of probe speed on probe displacement and surface area. The relationship between formulation hardness and probe displacement was linear and was dependent on probe speed. Furthermore, the proportionality constant (gel strength) increased as a function of PVP concentration. The relationship between formulation hardness and diameter ratio was biphasic and was statistically defined by two linear relationships relating to diameter ratios from 0 to 0.4 and from 0.4 to 0.563. The dramatically increased hardness, associated with diameter ratios in excess of 0.4, was accredited to boundary effects, that is, the effect of the container wall on product flow. Using dimensional analysis, the hardness and probe displacement in TPA were mathematically transformed into corresponding rheological parameters, namely shearing stress and rate of shear, thereby allowing the application of the power law (??=?k?n) to textural data. Importantly, the consistencies (k) of the formulations, calculated using transformed textural data, were statistically similar to those obtained using flow rheometry. In conclusion, this study has, firstly, characterized the relationships between textural data and two key instrumental parameters in TPA and, secondly, described a method by which rheological information may be derived using this technique. This will enable a greater application of TPA for the rheological characterization of pharmaceutical gels and, in addition, will enable efficient interpretation of textural data under different experimental parameters.