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At least 19 records

Membrane synthesis via in-situ pore formation in silica gels through dynamic miscibility with soybean oil

The dynamic immiscibility between vegetable oil and organic silica precursors during sol-gel synthesis was used to tailor the microstructure of gels made with tetraethoxysilane (TEOS) or tetraethoxysilane+methyltrimethoxysilane (MTMS). Vegetable oil was investigated as an environmentally friendly and cheaper alternative to many other porogens. Oil concentrations of 9.09 v/v% and 33.33 v/v% were studied. For both TEOS and TEOS+MTMS gels, the miscibility of the oil and precursor decreases as the silica gel network forms, leading to oil-rich regions within the silica matrix. Gels containing MTMS maintained partial miscibility with the oil during gel formation due to the non-hydrolysable methyl groups on the MTMS. The pore structure of MTMS gels appeared more interconnected compared to the isolated pores observed in gels made with only TEOS. To create membranes with hierarchical pore structures, solvent exchanges were performed on gels or dried gels (i.e., xerogels) were calcined. The effect of the methyl group was also observed in the results of the time sweep rheology, as the addition of oil to the TEOS+MTMS gels caused an increase in the time to form the spanning gel. The trend was the opposite for oil additions to TEOS gels, which only contained polar groups. Xerogel membranes made with TEOS+MTMS had higher specific surface areas (SSAs) than those made with TEOS. For oil concentrations of 33.33 v/v%, xerogels made from TEOS+MTMS had an average SSA of 1068 + 113 m2 g-1, an order of magnitude higher than the average SSA of 103 + 6 m2 g-1 for xerogels made with TEOS.

sol-gel, dynamic immiscibility, oil-alkoxide inter↗

Gels and gel-derived glasses in the Na2O-B2O3-SiO2 system

The containerless melting of high-purity multicomponent homogeneous gels and gel-monoliths offers a unique approach to making ultrapure multicomponent optical glasses in the reduced gravity environment of space. Procedures for preparing and characterizing gels and gel-derived glasses in the Na2O-B2O3-SiO2 system are described. Preparation is based on the polymerization reactions of alkoxysilane with trimethyl borate or boric acid and a suitable sodium compound. The chemistry of the gelling process is discussed in terms of process parameters and the gel compositions. The physicochemical nature of gels prepared by three different procedures were found to be significantly different. IR absorption spectra indicate finite differences in the molecular structures of the different gels. The melting of the gel powders and the transformation of porous gel-monoliths to transparent 'glass' without melting are described.

Mukherjee, S. P.↗

Gels and gel-derived glasses in the system Na2O-B2O3-SiO2

The containerless melting of high-purity multicomponent homogeneous gels and gel monoliths offers a unique approach to making ultrapure multicomponent optical glasses in the reduced gravity environment of space. Procedures for preparing and characterizing gels and gel-derived glasses in the system Na2O-B2O3-SiO2 are described. Preparation is based on the polymerization reactions of alkoxysilane with trimethyl borate or boric acid and a suitable sodium compound. The chemistry of the gelling process is discussed in terms of process parameters and the gel compositions. The physicochemical nature of gels prepared by three different procedures was found to be significantly different. Infrared absorption spectra indicate finite differences in the molecular structures of the different gels. The melting of the gel powders and the transformation of porous gel monoliths to transparent 'glass' without melting are described.

Mukherjee, S. P.↗

Homogeneity of gels and gel-derived glasses

The significance and implications of gel preparation procedures in controlling the homogeneity of multicomponent oxide gels are discussed. The role of physicochemical factors such as the structure and chemical reactivities of alkoxides, the formation of double-metal alkoxides, and the nature of solvent(s) are critically analyzed in the context of homogeneity of gels during gelation. Three procedures for preparing gels in the SiO2-B2O3-Na2O system are examined in the context of cation distribution. Light scattering results for glasses in the SiO2-B2O3-Na2O system prepared by both the gel technique and the conventional technique are examined.

Mukherjee, S. P.↗

Structural studies of gels and gel-glasses in the SiO2-GeO2 system using vibrational spectroscopy

GeO2 gel and gels in the SiO2-GeO2 system synthesized by the hydrolytic polycondensation of metal alkoxides have been studied by infrared and Raman spectroscopic techniques. The molecular structures, hydroxyl contents, and crystallinity of gels and gel-glasses in relation to the thermal history and GeO2 concentration were investigated. The binary compositions having up to 70 mol percent GeO2 were examined.

Mukherjee, Shyama P.↗

Crosslinked Polyethyleneimine Gel Polymer Interface to Improve Cycling Stability of RFBs

Redox flow batteries are considered a promising technology for grid energy storage. However, capacity decay caused by crossover of active materials is a universal challenge for many flow battery systems, which are based on various chemistries. In this paper, using the vanadium redox flow battery as an example, we demonstrate a new gel polymer interface (GPI) consisting of crosslinked polyethyleneimine with a large amount of amino and carboxylic acid groups introduced between the positive electrode and the membrane. The GPI functions as a key component to prevent vanadium ions from crossing the membrane, thus supporting stable long-term cycling. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to investigate the effect of GPI on the electrochemical properties of graphitic carbon electrodes (GCFs) and redox reaction of catholyte. X-ray photoelectron spectroscopy (XPS) and 1 H nuclear magnetic resonance (NMR) spectra demonstrated that the crosslinked GPI is chemically stable for 100 cycles without dissolution of polymers and swelling in the strong acidic electrolytes. Results from inductively coupled plasma mass spectrometry (ICP-MS), Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDX) spectroscopy proved that the GPI is effective in maintaining the concentration of vanadium species in their respective half-cells, resulting in improved cycling stability because of it prevents active species from crossing the membrane and stabilizes the oxidation states of active species.

Lim, Hyung-Seok↗

Cellulosic gels, films and composites including the gels, and methods of forming same

Disclosed are cellulose-based 5 flexible aerogels and xerogels containing bacterial cellulose nanorods, ribbons, fibers, and the like, wherein the gels have tunable optical, heat transfer, and stiffness properties. Further disclosed are highly transparent and flexible cellulose nanofiber-polysiloxane composite aerogels featuring enhanced mechanical robustness, tunable optical anisotropy, and low thermal conductivity.

Smalyukh, Ivan I.↗

An energy-optimization method to study gel-swelling in confinement

Using our open-source programming environment Morpho, an energy-optimization method is developed to compute equilibrium shapes of an arbitrarily confined swollen hydrogel. The internal strains and contact forces are measured, probing its mechanics.

Joshi, Chaitanya↗

Tunable polyvinyl chloride (PVC) and thermoplastic polyurethane (TPU)-based soft polymer gel sensors

Abstract Polyvinyl chloride (PVC) gels have recently been found to exhibit mechanoelectrical transduction under mechanical deformation. These mechanoelectrical properties of PVC gels are largely uncharacterized and the underlying transduction mechanisms are currently unknown. These soft electroactive polymers have tunable properties such as modulus and response voltage based on physical dimensions and the amount of plasticizer content within the material making them ideal candidates for complaint sensors. This study aims to investigate PVC gels comprised of various plasticizers to further investigate underlying mechanisms of mechanoelectrical transduction and broaden possible sensing applications. Plasticizers used in this study include dibutyl adipate, dibutyl phthalate, dioctyl phthalate, otherwise known as bis(2-ethylhexyl) phthalate, diisodecyl adipate, and the environmentally friendly biodegradable plasticizer acetyl tributyl citrate (ATBC). ATBC is often used in cosmetics and food packaging applications and is even used as a food additive which may lead to future biocompatibility for these gel sensors. These plasticizers are used to produce PVC gel sensors that are experimentally tested for mechanoelectrical transduction properties and sensing performance. In this study, a Langmuir adsorptive model is fit to the collected mechanoelectrical transduction data. These results are also nondimensionalized and compared to the characteristic dimensionless Langmuir adsorptive model. This simple model agrees very well with the experimental data. Additionally, a study on the mechanoelectrical transduction of an alternative polymer lattice structure, thermoplastic polyurethane (TPU), is discussed. This is a novel electroactive polymer investigated for mechanoelectrical transduction properties. This portion of the study aims to further knowledge of underlying mechanisms of mechanoelectrical transduction as well as show feasibility of additional lattices for soft polymer gel sensors. These TPU gel sensors show strikingly similar mechanoelectrical transduction properties to analogous PVC gels, insinuating that the polymer structure has a limited role in the underlying sensing mechanism and PVC itself is not unique to polymer gel sensing. The TPU-based soft polymer gel sensors however do display some level of mechanoelectrical hysteresis which may be attributed to viscoelastic properties and display a small amount of fatigue possibly due to exudation of liquid plasticizer. This study provides further characterization of mechanoelectrical response for varying plasticizers, provides a theoretical framework for underlying mechanisms, and displays the potential for further polymeric gel sensors.

Instruments & Instrumentation↗

Topological Data Analysis for Particulate Gels

Soft gels, formed via the self-assembly of particulate materials, exhibit intricate multiscale structures that provide them with flexibility and resilience when subjected to external stresses. Here, this work combines particle simulations and topological data analysis (TDA) to characterize the complex multiscale structure of soft gels. Our TDA analysis focuses on the use of the Euler characteristic, which is an interpretable and computationally scalable topological descriptor that is combined with filtration operations to obtain information on the geometric (local) and topological (global) structure of soft gels. We reduce the topological information obtained with TDA using principal component analysis (PCA) and show that this provides an informative low-dimensional representation of the gel structure. We use the proposed computational framework to investigate the influence of gel preparation (e.g., quench rate, volume fraction) on soft gel structure and to explore dynamic deformations that emerge under oscillatory shear in various response regimes (linear, nonlinear, and flow). Our analysis provides evidence of the existence of hierarchical structures in soft gels, which are not easily identifiable otherwise. Moreover, our analysis reveals direct correlations between topological changes of the gel structure under deformation and mechanical phenomena distinctive of gel materials, such as stiffening and yielding. In summary, we show that TDA facilitates the mathematical representation, quantification, and analysis of soft gel structures, extending traditional network analysis methods to capture both local and global organization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal-silica sol-gel materials

The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

Stiegman, Albert E.↗

A study of electroactive polyvinyl chloride (PVC) gel actuators through the use of the electric modulus formalism and cyclic linear voltage sweeps

The conductivity and dielectric properties are integral to the function of polyvinyl chloride (PVC) gel actuators. The frequency-dependent properties of PVC gel actuators are investigated here in terms of their impedance, permittivity, and for the first time, electric modulus. The data shows that PVC gels’ conductive properties are just as, if not more, important as their dielectric properties in electromechanical transduction applications. The electrode polarization (EP) and its impact on the impedance and dielectric spectra of PVC gels, as well as the developed asymmetric space charge at the anode, are discussed. The electric modulus and tan δ spectra are used for the fitting of Cole-Cole (CC) and Debye relaxation models for gels of varying plasticizer content. The electrostatic adhesive force for PVC gels of varying plasticizer is also measured, indicating large electrostatic adhesion (>2 N cm -2 ). A cyclic linear voltage sweep is used to clarify the dynamics of space charge within the gels. The peak current (associated with space charge development) is seen to be concurrent with the onset of mechanical deformation, showing the asymmetric charge as the origin of electromechanical transduction. Additionally, the maximum charge transferred (as measured by the integration of current over time) before space charge development is found to correlate with the electrostatic adhesive force measured for the gels, pointing to a new method of characterizing PVC gels for actuation.

Instruments & Instrumentation↗

Sol-Gel synthesis of MgO-SiO2 glass compositions having stable liquid-liquid immiscibility

MgO-SiO2 glasses containing up to 15 mol % MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol % MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol % MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol %) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗

Sol-gel synthesis of magnesium oxide-silicon dioxide glass compositions

MgO-SiO2 glasses containing up to 15 mol pct MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol pct MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol pct MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol pct) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water:TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, x ray diffraction, surface area and pore size distribution measurements.

Bansal, Narottam P.↗

Tissue simulating gel for medical research

A tissue simulating gel and a method for preparing the tissue simulating gel are disclosed. The tissue simulating gel is prepared by a process using water, gelatin, ethylene gylcol, and a cross-linking agent. In order to closely approximate the characteristics of the type of tissue being simulated, other material has been added to change the electrical, sound conducting, and wave scattering properties of the tissue simulating gel. The result of the entire process is a formulation that will not melt at the elevated temperatures involved in hyperthermia medical research. Furthermore, the tissue simulating gel will not support mold or bacterial growth, is of a sufficient mechanical strength to maintain a desired shape without a supporting shell, and is non-hardening and non-drying. Substances were injected into the tissue simulating gel prior to the setting-up thereof just as they could be injected into actual tissue, and the tissue simulating gel is translucent so as to permit visual inspection of its interior. A polyurethane spray often used for coating circuit boards can be applied to the surface of the tissue simulating gel to give a texture similar to human skin, making the tissue simulating gel easier to handle and contributing to its longevity.

Companion, John A.↗

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by the sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water: TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, X-ray diffraction, surface area and pore size distribution measurements.

Bansal, N. P.↗