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At least 19 records

Applying colloidal silica suspensions injection and sequential gelation to block vertical water flow in well annulus: laboratory testing on rheology, gelation, and injection

We evaluated the application of silica suspension injection and sequential gelation to block vertical water flow in the annuli of long-screened wells. First, we studied the viscosity, rheological behavior, and gelation performance of colloidal silica suspensions in batch tests. Then, we tested the injection of silica suspensions and the water flow blocking efficiency of the later formed silica gel in column and bench-scale sandbox experiments. Micron-sized fumed powder silica suspensions and nanosized silica suspensions recovered from geothermal fluids were tested in this work. Fumed silica suspensions showed shear thinning, while nanosized silica suspensions exhibited Newtonian flow behavior. During the gelation process, the nanosized silica suspension changed from a Newtonian fluid to a shear thinning fluid while increasing its overall viscosity. At comparable concentrations, the nanosized silica suspensions have much lower viscosity than that of the fumed silica suspensions. Increases in the Na + concentration and silica particle concentration in these suspensions shortened the gelation time. Silica suspension gelation in sand columns completely blocked the water flow and sustained the injection pressure up to 50 psig (344.7 kPa). A silica suspension was successfully injected into the target zone in the annulus of a bench-scale sandbox mimicking long-screened wells in the field. The silica gel formed in the annulus effectively blocked chemical transport through the gelled zone. Our research reveals that a process using silica suspension injection and sequential gelation technology is promising for blocking the vertical water flow and chemical transport through the filter pack in targeted zones within the annulus of long-screened well systems.

54 ENVIRONMENTAL SCIENCES↗

Reversible Physical Gelation of Thermotropic Liquid Crystals Driven by Nanoplate Self-Assembly

Physically gelled soft materials, driven by the self-assembly of low-molecular-mass gelators (LMGs), have emerged as a platform for designing advanced gels that exhibit reversible gelation and property tunability. Liquid crystal (LC) gels are of great interest due to their supramolecular orderings as gel hosts and their enhanced electro-optical properties. In this study, we demonstrate the physical gelation of a nematic LC driven by nanoplate self-assembly, expanding the concept of gelators from small molecules to nanoparticles. These nanoplates are functionalized with promesogenic ligands and form a fibrillar network in LCs with face-to-face interplate stacking, resembling LMGs. The critical gelation volume fraction in the tilt test is only 0.14 v %, comparable to values reported for LMGs. Rheological analyses confirm viscoelastic properties characteristic of gelation. In situ small-angle X-ray scattering (SAXS) characterizes the formation of nanoplate networks in the LC with decreasing temperature, wherein LC mesogens become trapped in pores. Molecular dynamics (MD) simulations reveal that the interaction between ligand-coated nanoplates and LC-forming mesogens induces a multidomain LC structure, increasing friction between LC domains and stabilizing the gel. This study establishes direct relationships among molecular interactions, nanostructures, and mechanical properties in physically gelled LCs. In conclusion, the findings inspire the future gelator design of both LMGs and nanoplates, with potential applicability in bioscaffold engineering and liquid crystalline nanocomposites.

36 MATERIALS SCIENCE↗

Computational Prediction of Coiled–Coil Protein Gelation Dynamics and Structure

Protein hydrogels represent an important and growing biomaterial for a multitude of applications, including diagnostics and drug delivery. We have previously explored the ability to engineer the thermoresponsive supramolecular assembly of coiled–coil proteins into hydrogels with varying gelation properties, where we have defined important parameters in the coiled–coil hydrogel design. Using Rosetta energy scores and Poisson–Boltzmann electrostatic energies, we iterate a computational design strategy to predict the gelation of coiled–coil proteins while simultaneously exploring five new coiled–coil protein hydrogel sequences. Provided this library, we explore the impact of in silico energies on structure and gelation kinetics, where we also reveal a range of blue autofluorescence that enables hydrogel disassembly and recovery. As a result of this library, we identify the new coiled–coil hydrogel sequence, Q5, capable of gelation within 24 h at 4 °C, a more than 2-fold increase over that of our previous iteration Q2. The fast gelation time of Q5 enables the assessment of structural transition in real time using small-angle X-ray scattering (SAXS) that is correlated to coarse-grained and atomistic molecular dynamics simulations revealing the supramolecular assembling behavior of coiled–coils toward nanofiber assembly and gelation. This work represents the first system of hydrogels with predictable self-assembly, autofluorescent capability, and a molecular model of coiled–coil fiber formation.

36 MATERIALS SCIENCE↗

Foundational insights into the mechanical and molecular evolution of porcine skin gelatin during gelation

Gelatin is a widely used material in biomedical fields, particularly in regenerative medicine and tissue engineering, due to its biocompatibility and versatile properties. While prior research has explored methods to enhance gelatin's mechanical strength and stability, fundamental studies on gelatin, specifically its curing process, mechanical stiffness, and chemical evolution during gelation, remain limited. This study uses ultrasonic testing and Fourier Transform Infrared Spectroscopy (FTIR) to examine gelatin's stiffness and molecular changes during gelation. Samples of 175 and 300 Porcine Skin Bloom Strength Gelatin at concentrations of 2% and 6% (w/v) were analyzed. Through transmission ultrasonic testing helped identify key transition points in gelation, with higher concentrations exhibiting delayed transitions. FTIR revealed that C-N bond formation peaks early while N-H bond deformation persists. A correlation emerged between sound speed and peak absorbance, suggesting that changes in molecular mobility may contribute to the observed sound speed behavior during periods of active bond formation. However, as gelation continues, fewer bonding components may be available, potentially decreasing molecular movement and contributing to the observed increase in sound speed. These findings provide insights into gelatin's mechanical and chemical evolution, offering a framework for improved control over its gelation kinetics. Swept-Frequency Acoustic Interferometry (SFAI) was performed at the end of the curing process to measure the sound speed, enabling the calculation of the bulk moduli of the gelatin samples. The combined use of ultrasonic and FTIR testing provides a non-destructive method for characterizing gelatin and other biomaterials. This approach advances understanding of gelatin curing behavior and supports the development of safer biomaterials with tailored mechanical properties for various applications such as tissue engineering and regenerative medicine.

Biomaterials↗

Three-step colloidal gelation revealed by time-resolved x-ray photon correlation spectroscopy

The gelation of PEGylated gold nanoparticles dispersed in a glycerol–water mixture is probed in situ by x-ray photon correlation spectroscopy. Following the evolution of structure and dynamics over 10 4 s, a three-step gelation process is found. First, a simultaneous increase of the Ornstein–Zernike length ξ and slowdown of dynamics is characterized by an anomalous q-dependence of the relaxation times of τ ∝q -6 and strongly stretched intermediate scattering functions. After the structure of the gel network has been established, evidenced by a constant ξ, the dynamics show aging during the second gelation step accompanied by a change toward ballistic dynamics with τ ∝ q -1 and compressed correlation functions. In the third step, aging continues after the arrest of particle motion. Our observations further suggest that gelation is characterized by stress release as evidenced by anisotropic dynamics once gelation sets in.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Use of a Pressurized Water Treatment to Prevent Cracking of Internal Gelation Sol-Gel Microspheres

Pressurized water treatments were investigated as a means to prevent cracking of internal gelation sol-gel microspheres upon drying and heating. A batch of gelled cerium oxide microspheres was prepared, split into two samples that were processed with and without a pressurized water treatment, and dried in air at room temperature. Thermal gravimetric analysis was used to compare the mass loss profiles between the two samples and to understand volatile emissions from cerium oxide microspheres during heat treatments up to 600 °C. Microspheres that were processed without a pressurized water treatment lost approximately 4.6 times more mass upon heating than microspheres that were subjected to a pressurized water treatment. Comparison of the cracking behavior of microspheres prepared with and without a pressurized water treatment indicated that microspheres subjected to a pressurized water treatment were virtually crack-free after heat treatments. Conversely, microspheres processed without a pressurized water treatment, which is typical of traditional washing processes, exhibited extensive cracking. Analysis of residues dried from pressurized water treatment effluents indicated that hexamethylenetetramine and urea, which are excess reactants from the internal gelation process, were removed from gelled microspheres during the pressurized water treatment step. Traditional processing methods for preparing internal gelation microspheres use specific feed solution and gelation parameters to reduce subsequent cracking upon drying and heating. Results from this study indicate that more aggressive gel-forming conditions may be used to produce crack-free microspheres, if a pressurized water treatment step is included after washing and before air-drying.

cerium oxide, internal gelation, microsphere, TRIS↗

Trichloroethylene replacements for the cleaning of silicone oil used in the internal gelation process

Silicone oil continues to be used as a gelation medium for internal gelation process. Typically, the silicone oil has been removed from the gel spheres using trichloroethylene (TCE) washes. However, TCE is no longer a viable option for large-scale operations because of environmental issues, health concerns, and disposal costs. Furthermore, during the development of a large gelation system at the Y-12 National Security Complex, two new TCE wash replacements were identified. NuSolv SOR-C and FluoSolv WS were used in a number of uranium runs and found to effectively remove silicone oil. NuSolv SOR-C was determined to be the best option.

36 MATERIALS SCIENCE↗

Orthogonal Gelations to Synthesize Core–Shell Hydrogels Loaded with Nanoemulsion‐Templated Drug Nanoparticles for Versatile Oral Drug Delivery

Hydrophobic active pharmaceutical ingredients (APIs) are ubiquitous in the drug development pipeline, but their poor bioavailability often prevents their translation into drug products. Industrial processes to formulate hydrophobic APIs are expensive, difficult to optimize, and not flexible enough to incorporate customizable drug release profiles into drug products. Here, a novel, dual-responsive gelation process that exploits orthogonal thermo-responsive and ion-responsive gelations is introduced. This one-step “dual gelation” synthesizes core–shell (methylcellulose-alginate) hydrogel particles and encapsulates drug-laden nanoemulsions in the hydrogel matrices. In situ crystallization templates drug nanocrystals inside the polymeric core, while a kinetically stable amorphous solid dispersion is templated in the shell. Drug release is explored as a function of particle geometry, and programmable release is demonstrated for various therapeutic applications including delayed pulsatile release and sequential release of a model fixed-dose combination drug product of ibuprofen and fenofibrate. Independent control over drug loading between the shell and the core is demonstrated. This formulation approach is shown to be a flexible process to develop drug products with biocompatible materials, facile synthesis, and precise drug release performance. This work suggests and applies a novel method to leverage orthogonal gel chemistries to generate functional core–shell hydrogel particles.

60 APPLIED LIFE SCIENCES↗

Influence of TMAO as co-solvent on the gelation of silica-PNIPAm core-shell nanogels at intermediate volume fractions

We study the structure and dynamics of poly(N-isopropylacrylamide) (PNIPAm) core-shell nanogels dispersed in aqueous trimethylamine N-oxide (TMAO) solutions by means of smallangle X-ray scattering and X-ray photon correlation spectroscopy (XPCS). Upon increasing the temperature above the lower critical solution temperature of PNIPAm at 33°C, a colloidal gel is formed as identified by an increase of I(q) at small q as well as a slowing down of sample dynamics by various orders of magnitude. With increasing TMAO concentration the gelation transition shifts linearly to lower temperatures. Above a TMAO concentration of approximately 0.40 mol/L corresponding to a 1:1 ratio of TMAO and NIPAm groups, collapsed PNIPAm states are found for all temperatures without any gelation transition. This suggests that reduction of PNIPAm-water hydrogen bonds due to the presence of TMAO results in a stabilisation of the collapsed PNIPAm state and suppresses gelation of the nanogel.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering supramolecular and polymer-like behavior in metallogels: real-time insights into temperature-modulated gelation and rapid self-assembly dynamics

Bis(pyridyl) urea-based gelators, namely L2 and its isomeric mixture ( L1 + L2 ), are known to self-assemble into 1D architectures capable of inducing supramolecular gelation. Coordination with metal ions such as Ag( I ), Cu( II ), and Fe( III ) introduces structural reinforcement, enabling the formation of distinct 3D networks governed by metal-specific coordination geometries. Here, we present a comprehensive investigation into the temperature-responsive behavior (20–60 °C) of L2 and L1 + L2 , both in the absence and presence of Ag( I ), Dy( III ), Fe( III ), Cu( II ), and Ho( III ), using real-time small-angle neutron scattering (SANS). To probe long-term structural evolution/kinetics of self-assembly, real-time small-angle X-ray scattering (SAXS) was employed on L2 + Ag gels, complemented by differential scanning calorimetry (DSC) to evaluate thermal transitions. Our results reveal strikingly divergent gelation behaviors: L2 forms a highly rigid, covalent polymer-like network, while L1 + L2 exhibits remarkable thermal adaptability. Upon metal coordination, the assemblies exhibit pronounced crystallinity and exceptional thermal stability, as evidenced by persistent Bragg reflections and invariant d-spacings. Intriguingly, L2 : Fe (2 : 1) and L1 : L2 : Fe (0.5 : 0.5 : 1) in acetonitrile-d 3 (ACN-d 3 ) deviate from this trend, forming thermally labile amorphous gels. These systems show a complete loss of crystalline order, reduced Porod exponents—indicative of collapsed or branched fiber morphologies—and prominent melting and glass transition events in DSC. Fitting SANS and SAXS data to the correlation length model unveiled insightful nanostructural features. While most systems displayed minimal temperature-induced variation in mesh size or surface morphology, L2 : Ag in dimethyl sulfoxide-d 6 (DMSO-d 6 )/D 2 O and L2 : Fe (1 : 1) in ACN-d 3 exhibited a rare combination of thermally stable correlation lengths and increasing high- q exponents—strongly suggesting progressive fiber densification or surface smoothing within a robust gel framework. These findings highlight the tunability and structural resilience of supramolecular gels through precise control of ligand architecture, metal coordination, and temperature, offering valuable design principles for functional soft materials.

Pajoubpong, Jinnipha [Univ. of Cincinnati, OH (Uni↗

Impurity Levels in Cerium Oxide Microspheres Prepared by Internal Gelation Sol-Gel Methods

Impurity levels were measured in cerium oxide microspheres fabricated by modified internal gelation sol-gel methods. A combination of glow discharge mass spectrometry, electron impact mass spectrometry, combustion gas analysis and instrumental gas analysis were used to assess a wide range of potential elemental impurities. Low concentrations of carbon, nitrogen, and hydrogen impurities in microspheres showed a dependence on how microspheres were washed. Silicon impurities are believed to derive from silicone oil used during sol-gel processing. Spheres washed by the preferred approach had impurity levels below 100 ppm for all elements tested. For applications such as nuclear fuels, sol-gel methods could meet purity specifications as long as metal nitrate feed solutions of sufficient purity are used and microspheres are washed appropriately. In this study, cerium was used as a surrogate for plutonium-238, which is used in radioisotope power systems as a heat source, to determine whether carbon or other impurities were concentrated during internal gelation processing and remained after heat treatments. Analyses indicated low concentrations of impurities in cerium oxide microspheres after sintering steps that were well below documented limits for plutonium-238 oxide fuels. Modified washing methods, combined with a pressurized water treatment, resulted in sintered cerium oxide sol-gel microspheres with low impurity levels.

cerium oxide, sol-gel, internal gelation, microsph↗

Effects of a Pressurized Water Treatment on Internal Gelation Sol-Gel Microspheres

Based on previous observations that a pressurized water treatment (PWT) prevented cracking of sol-gel microspheres, we investigated the effects of a PWT on microsphere crystallinity, density, and specific surface area (SSA). Results were used to determine how a PWT alters the properties of microspheres upon drying and heating. Microspheres with diameters near 100-200 µm were prepared with and without a PWT and measured using x-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption (BET), and pycnometry. Properties of air-dried microspheres processed with and without a PWT are compared. Additionally, the properties of microspheres processed using a PWT are reported after heating to 150 °C, 450 °C, 750 °C, 1050 °C, and 1350 °C. X-ray diffraction measurements indicate that the PWT step improves the crystallinity of air-dried microspheres. XRD data was also used to calculate crystallite size, which increases with higher heat treatment temperatures. TEM images support crystallite size calculations from XRD data and provide an indication of the range of crystallite sizes, particularly for samples processed at higher temperatures where crystallite sizes are too large for estimation using the Scherrer formula. Density and SSA measurements performed as a function of heat treatment temperature indicate that a PWT increases the density of air-dried microspheres, creates a pore network, and that significant densification occurs between 450 - 750 °C. These results may be used to inform decisions on internal gelation flowsheet parameters to optimize the microsphere formation and gelation step, prevent microsphere cracking, and produce microspheres suitable for subsequent coating operations or pressing into pellets.

cerium oxide, TRISO, internal gelation, nuclear fu↗

Dynamics of Polymerization and Gelation in Epoxy Nanocomposites via X-ray Photon Correlation Spectroscopy

The details of the curing process of epoxy resins are notoriously difficult to ascertain, hampering polymer matrix composite manufacturing. Here, the curing of a series of six epoxy resins containing dilute spherical nanoparticles was investigated via X-ray photon correlation spectroscopy (XPCS). The resin formulation was varied to achieve a range of crosslink densities and topologies. Prior to gelation, the viscosities obtained from XPCS agreed with bulk rheology. A clear dynamic transition was detected in all samples, where the q-scaling changes from approximately q2 .2 to q 1 , indicating a transition from sub-diffusive to ballistic-like nanoparticle motion. For the samples with a high crosslink density, this change was abrupt and coincided with gelation, and there was no evidence of crosslink heterogeneity. Chain entanglement played a role in the transition for samples with lower crosslink density. Finally, this work reveals the potential of XPCS to deliver new quantitative insights into the curing process of thermosetting resins.

36 MATERIALS SCIENCE↗

Characterization of zirconium carbide microspheres synthesized via internal gelation

Microspheres of zirconium carbide with grain size 40-320 nm were synthesized using internal gelation techniques and characterized by scanning electron microscopy, synchrotron X-ray diffraction, and neutron total scattering. Compared with a polycrystalline benchmark ZrC sample prepared by plasma vapor phase deposition, the microspheres display lower variance in grain size and considerably lower microstrain representative of a more homogenous internal microstructure. However, excess carbon was present in the microspheres, evident in both the X-ray and neutron diffraction data as well as a corresponding hypostoichiometric ZrC phase. Furthermore, the excess carbon phase is assumed to be pockets of carbon that remained unreacted through the combined internal gelation and subsequent carbothermic reduction synthesis process. Atomic-scale structural characterization with neutron PDF analysis confirmed the presence of localized nano-sized domains of graphite-like carbon material.

36 MATERIALS SCIENCE↗

Egg yolk as a model for gelation: From rheometry to flow physics

Egg yolks are an excellent model for studying sol-gel transitions, particularly the power law viscoelasticity that defines the critical point of gelation. However, prior studies lack comprehensive datasets and fail to visualize flow behavior linked to temperature and time-dependent linear and nonlinear rheology. Here, we present a detailed dataset characterizing egg yolk viscoelasticity across temperature, time, and forcing amplitude using oscillatory shear, step strain, step stress, and constant high strain rate. Novel protorheology visualizations link rheological properties with observable flow behavior. Our findings highlight the nuanced determination of the critical gel point, emphasizing observation timescale dependencies. We compare methods to identify critical temperatures for gelation, including power law viscoelasticity, moduli crossover, diverging zero-shear viscosity, and emerging equilibrium elastic modulus, while visualizing flow consequences near these transitions. Egg yolk is an accessible, realistic, and nontoxic material relevant to the physicist and the chef alike, making it ideal for understanding the rheology of critical gels. By integrating protorheology photos and videos with rigorous rheometric data, we deepen the understanding of critical gels, with broader impacts for studying other materials with sol-gel transitions.

Marsh, Maxwell C. [Department of Mechanical Scienc↗

Vibrational Spectroscopic Monitoring of the Gelation Transition in Nafion Ionomer Dispersions

Infrared and Raman spectroscopy techniques were applied to investigate the drying and aggregation behavior of Nafion ionomer particles dispersed in aqueous solution. Gravimetric measurements aided the identification of gel-phase development within a series of time-resolved spectra that tracked transformations of a dispersion sample during solvent evaporation. A spectral band characteristic of ionomer sidechain end group vibration provided a quantitative probe of the dispersion-to-gel change. For sets of attenuated total reflection Fourier transform infrared (ATR FT-IR) spectra, adherence to Beer's law was attributed to the relatively constant refractive index in the frequency region of hydrated –SO$^{–}_{3}$ group vibrations as fluorocarbon-rich ionomer regions aggregate in forming the structural framework of membranes and thin films. Although vibrational bands associated with ionomer backbone CF 2 stretching vibrations were affected by distortion characteristic of wavelength-dependent refractive index change within a sample, the onset of band distortion signaled gel formation and coincided with ionomer mass % values just below the critical gelation point for Nafion aqueous dispersions. Similar temporal behavior was observed in confocal Raman microscopy experiments that monitored the formation of a thin ionomer film from an individual dispersion droplet. For the ATR FT-IR spectroscopy and confocal Raman microscopy techniques, intensity in the water H–O–H bending vibrational band dropped sharply at the ionomer critical gelation point and displayed a time dependence consistent with changes in water content derived from gravimetric measurements. The reported studies lay groundwork for examining the impact of dispersing solvents and above-ambient temperatures on fluorinated ionomer transformations that influence structural properties of dispersion-cast membranes and thin films.

36 MATERIALS SCIENCE↗

Internal-Gelation Production of Uranium Oxide Sol-Gel Particles for Forensic Applications

The purpose of this project was to develop and demonstrate a novel method for the production of uranium oxide microsphere particles with tunable chemical compositions via a sol-gel process using a 3D-printer setup. These particles can serve several purposes in research and development as a forensic training tool or as standard reference materials. A key component of the project was to demonstrate the ability to control physical and chemical parameters of the particles created. First, we demonstrated the ability to employ an internal gelation sol-gel process to create individual uranium oxide particles. The particles were successfully dispensed using a unique 3D-printing setup onto a substrate to react and then were collected and thermally processed. A series of temperatures for the annealing process was tested on individual samples to investigate the effect on the sol-gel chemical composition and physical integrity. Next, we demonstrated the ability to control matrix composition of the particles by separately incorporating fission product isotopes as well as Np-237 into the sol-gel solution. It was shown by gamma-ray spectroscopy that these matrix elements were successfully retained during the gelation process. We studied the retention of the elements across a series of annealing temperatures. Additionally, we demonstrated the ability to quantitatively control the isotopic composition of the particles by altering the U-237/U-238 ratio to a controlled value. Finally, X-ray diffraction analysis (XRD) was used to investigate the oxidation state of the sol-gel after annealing at different temperatures.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Anticipating gelation and vitrification with medium amplitude parallel superposition (MAPS) rheology and artificial neural networks

Abstract Anticipating qualitative changes in the rheological response of complex fluids (e.g., a gelation or vitrification transition) is an important capability for processing operations that utilize such materials in real-world environments. One class of complex fluids that exhibits distinct rheological states are soft glassy materials such as colloidal gels and clay dispersions, which can be well characterized by the soft glassy rheology (SGR) model. We first solve the model equations for the time-dependent, weakly nonlinear response of the SGR model. With this analytical solution, we show that the weak nonlinearities measured via medium amplitude parallel superposition (MAPS) rheology can be used to anticipate the rheological aging transitions in the linear response of soft glassy materials. This is a rheological version of a technique called structural health monitoring used widely in civil and aerospace engineering. We design and train artificial neural networks (ANNs) that are capable of quickly inferring the parameters of the SGR model from the results of sequential MAPS experiments. The combination of these data-rich experiments and machine learning tools to provide a surrogate for computationally expensive viscoelastic constitutive equations allows for rapid experimental characterization of the rheological state of soft glassy materials. We apply this technique to an aging dispersion of Laponite ® clay particles approaching the gel point and demonstrate that a trained ANN can provide real-time detection of transitions in the nonlinear response well in advance of incipient changes in the linear viscoelastic response of the system.

Lennon, Kyle R. (ORCID:0000000212515461)↗