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At least 559 records · Page 31

Methods of making permeable aerogels

Methods of making permeable aerogels (100) can include providing a sol mixture (110) comprising an organic scaffold, an inorganic aerogel precursor, and a first solvent. The organic scaffold can be insoluble in the first solvent. The sol mixture can react to form a gel (120) such that an interconnected channel network is formed which is at least partially defined by the organic scaffold. The first solvent in the gel can be exchanged (130) with a second solvent. The second solvent can dissolve the organic scaffold to expose the interconnected channel network. The gel can be dried (140) to form the permeable aerogel.

Carlson, Krista↗

High efficiency active environmental sampling of chemical traces

A method of sample collection includes collecting an analyte from a sampling surface using a rapidly curable liquid gel comprising one or more metal particles; co-aggregating the one or more metal particles from the rapidly curable liquid gel and the analyte from the sampling surface; and rapidly curing the rapidly curable liquid gel. The composition and sample preparation conditions may facilitate improved collection efficiency of analytes during environmental and forensic evidence sampling. In addition, the composition and sample preparation conditions may facilitate enhanced detection and identification of the analyte using e.g., Surface Enhanced Raman Spectrometry (SERS).

Junghans, Ann↗

Purification and properties of a dissimilatory nitrate reductase from Haloferax denitrificans

A membrane-bound nitrate reductase (nitrite:(acceptor) oxidoreductase, EC 1.7.99.4) from the extremely halophilic bacterium Haloferax denitrificans was solubilized by incubating membranes in buffer lacking NaCl and purified by DEAE, hydroxylapatite, and Sepharose 6B gel filtration chromatography. The purified nitrate reductase reduced chlorate and was inhibited by azide and cyanide. Preincubating the enzyme with cyanide increased the extent of inhibition which in turn was intensified when dithionite was present. Although cyanide was a noncompetitive inhibitor with respect to nitrate, nitrate protected against inhibition. The enzyme, as isolated, was composed of two subunits (Mr 116,000 and 60,000) and behaved as a dimer during gel filtration (Mr 380,000). Unlike other halobacterial enzymes, this nitrate reductase was most active, as well as stable, in the absence of salt.

Halobacteriaceae/enzymology↗

Static and Dynamic Gradient Based Directional Transportation of Neutral Molecules in Swollen Polymer Films

Abstract Materials which selectively transport molecules offer powerful opportunities for concentrating and separating chemical agents. Here, utilizing static and dynamic chemical gradients, transport of molecules within swollen crosslinked polymers is demonstrated. Using an ≈200 μm static hydroxyl to hexyl gradient, the neutral ambipolar nerve agent surrogate diethyl (cyanomethyl)phosphonate (DECP) is directionally transported and concentrated 60‐fold within 4 hours. To accelerate transport kinetics, a dynamic gradient (a “travelling wave”) is utilized. Here, the non‐polar dye pyrene was transported. The dynamic gradient is generated by an ion exchange process triggered by the localized introduction of an aqueous NaCl solution, which converts the gel from hydrophobic to hydrophilic. As the hydrophilic region expands, associated water enters the gel, and pyrene is pushed ahead of the expansion front. The dynamic gradient provides about 10‐fold faster transport kinetics than the static gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of alkali dosage and silicate modulus on autogenous shrinkage of alkali-activated slag cement paste

Autogenous shrinkage of alkali-activated slag cement (AASC) paste prepared with different levels of alkali dosage and silicate modulus (M{sub s}) is investigated. The results show that autogenous shrinkage of AASC paste increases at a decreasing rate with alkali dosage, which is attributed to enhanced capillary pore pressure and syneresis of C-A-S-H gels. Autogenous shrinkage of AASC paste with a constant alkali dosage increases as M{sub s} increases from 0.5 to 1.0, followed with a reduction as M{sub s} further increases to 2.0. Increasing M{sub s} initially enhances the capillary pore pressure due to the enhanced reaction degree, and promotes the formation of saturated capillary pores and viscoelasticity, which facilitates the autogenous shrinkage of AASC paste. However, excessive silicate in the activator retards the internal moisture consumption, and subsequently decreases the autogenous shrinkage of AASC paste. Furthermore, increasing M{sub s} can also intensify syneresis of C-A-S-H gels, contributing to the early-age autogenous shrinkage of AASC paste.

36 MATERIALS SCIENCE↗

Influence of the distribution of expansive sites in aggregates on microscopic damage caused by alkali-silica reaction: Insights into the mechanical origin of expansion

The origin of damage in concrete due to the alkali-silica reaction (ASR) is attributed to the expansion site in the aggregate. To investigate the cracking process of the aggregate during ASR and its consequences on concrete damage, the effect of the distribution of the expansive sites in the aggregate on ASR expansion and the crack patterns must be evaluated. Thus, in this study, a mesoscale discrete model was applied to ASR modeling to represent the propagation of cracking during ASR accurately. The distribution of the expansive sites in the aggregate was based on the gel pocket and reaction rim models, which are two ASR mechanisms reported in the literature. These two expansion models highlight the different crack patterns obtained based on the aggregate characteristics. Further, the expansion cracking processes determined based on the gel pocket and reaction rim models are consistent with the evolution of cracking with the expansion level.

36 MATERIALS SCIENCE↗

Comparison on the properties of ITZs in fly ash-based geopolymer and Portland cement concretes with equivalent flowability

Highlights: • Modelled ITZs can effectively avoid the effects caused by different factors and test locations of ITZ. • ITZ properties of PC and geopolymer concretes are compared based on equivalent flowability of binders. • Geopolymer ITZ exhibits stronger bonding than that of PC, and higher mechanical properties than geopolymer paste. • Strong ITZs in geopolymer concrete are attributed to the layer of gel-rich paste with dense microstructures. • Elastic modulus and hardness properties of ITZs in PC concrete are increased due to the CH crystals. This paper aims to compare the properties of interfacial transition zones (ITZs) in Portland cement (PC) concrete and geopolymer concrete. Portland cement and geopolymer pastes were designed with the equivalent flowability to provide similar mix and casting condition of ITZs. Two types of modelled ITZs were prepared to facilitate the nanoindentations across ITZs, microstructural characterization, and comparison on the properties of ITZs with less influential factors. The results showed that the interfacial bonding of ITZs between geopolymer matrix and aggregate is relatively stronger than the counterpart in the PC concrete. There is a high amount of crystalline hydration products in the ITZs of PC concrete, but a layer gel-rich paste with denser microstructures in the ITZs of geopolymer concrete. Additionally, the interface morphology and nanoindentation analysis indicate that the property of ITZs in the modelled geopolymer concrete is not poorer than that of the corresponding geopolymer paste.

36 MATERIALS SCIENCE↗

On the use of limestone calcined clay cement (LC3) in high-strength strain-hardening cement-based composites (HS-SHCC)

Highlights: • Use of LC{sup 3} slightly reduces flowability and shortens the setting time of fresh matrices. • Highly polymerized C-A-S-H gel and abundant ettringite benefit flexural strength of LC{sup 3}-matrices. • Use of LC{sup 3} enhances the bond strength between fiber and high-strength matrix. • LC{sup 3}-based HS-SHCC yields similar flexural performance as the composite with Portland cement. High-strength strain-hardening cement-based composites (HS-SHCC) demonstrate excellent mechanical and durability properties. However, high cement content typical to HS-SHCC results not only in high carbon footprint, but also in excessive hydration heat and severe autogenous shrinkage. In this investigation, Limestone Calcined Clay Cement (LC{sup 3}) was used to produce sustainable HS-SHCC. The LC{sup 3} substitution resulted in higher energy consumption during mixing and in shorter setting times of the fresh, plain matrices. Although the LC{sup 3} substitution slightly reduced the compressive strength, the formation of highly polymerized C-A-S-H gel and abundant ettringite benefited the flexural strength of the plain matrices. Additionally, single-fiber pullout experiments showed that the use of LC{sup 3} led to increased fiber-matrix bond strength and pullout energy. Finally, the replacement of Portland cement by LC{sup 3} resulted in HS-SHCC with similar mechanical performance to the reference composite, indicating a high potential for using LC{sup 3} in high-performance cement-based composites.

36 MATERIALS SCIENCE↗

Effect of rice husk ash-derived activator on the structural build-up of alkali activated materials

Highlights: • Filtered and unfiltered sodium silicate solutions were synthesised from RHA. • The dissolution efficiency of RHA in NaOH solution was 76.3%. • RHA-derived activator showed a structural build-up comparable to the commercial activator in AAM pastes. • The undissolved residues in the unfiltered RHA-derived activator increased the yield stress. • Comparable compressive strength and early age gel formation were observed from both commercial and RHA-derived solutions. Waste-derived sodium silicates (SSs) were synthesised from rice husk ash (RHA) to produce alkali activated materials (AAMs) using fly ash and slag as precursors. The effects of these SSs on the structural build-up were investigated by monitoring the evolution of the viscoelasticity, ultrasonic pulse waves, setting time, and infrared spectra. Two types of RHA derived SSs (filtered SS and unfiltered SS) were prepared to investigate the effect of the undissolved residue on the hardening process. The derived SS contained a large portion of monomer silicate species. The results showed that the structural build-up mechanism was comparable between the AAMs activated by the filtered SS and a commercial SS. The unfiltered SS increased the yield stress of the paste by up to 10 times. However, the residues in the unfiltered SS had insignificant impacts on the gel formation and compressive strength when using identical SiO{sub 2}/Na{sub 2}O and Na{sub 2}O/binder ratios in the mix design.

36 MATERIALS SCIENCE↗

Thermal Processing Conditions for the Synthesis of Near Theoretical Density Li 5 La 3 Ta 2 O 12 Ceramics for Ceramic Dual-Mode Detectors

A family of Li-containing garnet compounds, extensively investigated for Li-ion solid electrolyte applications, show great potential to be developed into transparent ceramic dual-mode scintillators. In particular, Li 5 La 3 Ta 2 O 12 (LLTaO) shows promise as an efficient dual-mode scintillator due to its high Li content, high density, non-hygroscopicity, and high effective-Z. Often the synthesis of LLTaO ceramics involves solid state processing techniques starting with oxide and carbonate powders, calcining, sintering for the removal of residual porosity, and post-processing. This study focuses on two objectives: (1) establishing thermal processing boundary conditions for a flexible alkoxide-based sol-gel method for synthesizing fine-grained powders; and (2), consolidating powders via hot-pressing to form high-density ceramics. In this study, near single-phase ceramics were achieved by hot-pressing sol-gel powders with varying amounts of excess Li. Rietveld refinements were used to analyze X-ray diffraction data and provide a quantitative evaluation of the phases present in the hot pressed ceramics. Some of the diffraction data showed large low angle peak asymmetry, suggesting the presence of two cubic Li 5 La 3 Ta 2 O 12 garnet phases with different lattice parameters. Depending on the synthesis and processing conditions, the refinement revealed ~ 90 wt% concentration of a phase with a ≈ 12.8 Å and ~ 10 wt% concentration of a phase with a ≈ 12.9 Å, indicating a remaining excess of Li in the hot pressed ceramics in the large lattice parameter phase. These synthesis experiments allowed for the determination of a baseline for Li loss during hot-pressing. X-ray excited radioluminescence and photoluminescence excitation and emission spectra were obtained from the hot pressed ceramics. In conclusion, the measured emission spectra featured broad tantalate emission and line emissions likely from a rare-earth impurity.

36 MATERIALS SCIENCE↗

A reactive electrochemomechanical theory for growth and remodeling of polyelectrolyte hydrogels and application to dynamic polymerization of $\text{DNA}$ hydrogels

Here this study develops a framework for growth and remodeling of active polyelectrolyte hydrogels that accounts for effects of compositional changes on the mechanical response. By developing a reactive electrochemomechanical theory, thermodynamical constraints upon reactive and remodeling processes are elucidated within a general framework that allows any number of chemical reactions to evolve the response of the gel and transfer mass and charge between constituents. Fully coupled, nonlinear constitutive relations are adopted for molar fluxes, allowing exploration of effects including cross-diffusion, electrophoresis, and electro-osmosis. A robust finite element implementation is developed in the open source FEBio software (febio.org) by exploiting an equivalence between electrochemomechanics and mixture theory. The implementation is verified against analytical solutions for free swelling, and a proper reduction to a prior chemomechanical theory is demonstrated for neutral gels swollen only by a solvent with no solutes. The theory and implementation are then applied to model the tunable large swelling achieved through dynamic polymerization of DNA crosslinkers seen in our recently developed experimental hydrogel system (Cangialosi et al., 2017). A novel constitutive model for reaction-driven evolution of the locking stretch λ L in a non-Gaussian mechanical free energy was developed, where the increasing concentration of DNA crosslinkers makes further swelling energetically favorable. With a single free parameter, excellent agreement was found between measured and predicted equilibrium swelling ratios. This study demonstrated the ability to extend the electrochemomechanical framework to include chemical reactions and composition-aware constitutive models, and showed that development of reactive models allows simulation of complex dynamic polymerization phenomena not treated before. The theoretical frame here can be further expanded in scope to incorporate additional non-ideal and nonlinear phenomena.

42 ENGINEERING↗

Modeling and mitigating fouling of microfiltration membranes for microalgae dewatering

Dewatering is energy-intensive for microalgae production, and microfiltration (MF) membranes are attractive because of their high energy efficiency. However, the membranes suffer from fouling by organic matter in the algae solutions, and there needs fundamental understanding of membrane fouling with actual algae solutions. Herein we thoroughly evaluate the dewatering performance of commercial polyethersulfone (PES) MF membranes using an integrated experiment and modeling approach. The effect of algae concentration, testing time, feed flow rate, and chemical cleaning on the dewatering performance and fouling-layer morphology are investigated. The fouling behavior can be successfully described using the Hermia and gel layer models with a gel concentration of 48 g/L for algae solutions. Furthermore, the PES membrane surface was grafted with hydrophilic zwitterions, which mitigated the fouling. For example, when challenged with 10 g/L algae solution in dead-end cells, the pristine and modified membrane exhibit water permeance of 80 and 170 L m – 2 h –1 bar –1 , respectively. Finally, three cycles of dewatering and NaOH cleaning were performed to demonstrate the promise of the MF membranes for practical dewatering application.

42 ENGINEERING↗

Effects of varying gelatin coating concentrations on RANKL induced osteoclastogenesis

Here, we assessed the effects of varying concentrations of gelatin coating on Receptor Activator of Nuclear Factor κ-B Ligand (RANKL)-induced RAW264.7 murine macrophage differentiation into osteoclast (OC) via osteoclastogenesis. The microstructures of coating surfaces with different concentrations of gelatin were examined by scanning electron microscopy and atomic force microscopy. Increased gelatin coating concentrations led to decreased gel rigidity but increased surface adhesion force attenuated OC differentiation and the decreased actin ring formation in RANKL-induced osteoclastogenesis. The decreased actin ring formation is associated with decreased lysosomal-associated membrane protein 1 (LAMP1) activity and bone resorption in the differentiated OCs with different gelatin coating concentrations as compared to the cells differentiated without gelatin coatings. In addition, increasing concentrations of gelatin coating attenuated the medium TGF-β1 protein levels and the expression levels of TGF-β and type-I (R1) and type-II (R2) TGF-β receptors in OCs, suggesting the gelatin-induced suppression of TGF-β signaling for the regulation of RNAKL-induced OC differentiation. Taken together, these findings showed that changes in gelatin coating concentrations, which were associated with altered gel thickness and substrate rigidity, might attenuate TGF-β signaling events to modulate OC differentiation and concomitant actin ring formation and bone matrix resorption in RANKL-induced osteoclastogenesis.

60 APPLIED LIFE SCIENCES↗

Finely tunable dynamical coloration using bicontinuous micrometer-domains

Nanostructures similar to those found in the vividly blue wings of Morpho butterflies and colorful photonic crystals enable structural color through constructive interference of light waves. Different from commonly studied structure-colored materials using periodic structures to manipulate optical properties, we report a previously unrecognized approach to precisely control the structural color and light transmission via a novel photonic colloidal gel without long-range order. Nanoparticles in this gel form micrometer-sized bicontinuous domains driven by the microphase separation of binary solvents. This approach enables dynamic coloration with a precise wavelength selectivity over a broad range of wavelengths extended well beyond the visible light that is not achievable with traditional methods. The dynamic wavelength selectivity is thermally tunable, reversible, and the material fabrication is easily scalable.

42 ENGINEERING↗

Microscopic dynamics underlying the stress relaxation of arrested soft materials

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches.

36 MATERIALS SCIENCE↗

Photonic curing for innovative fabrication of flexible metal oxide optoelectronics

Abstract Flexible optoelectronics, based on non-planar substrates, hold promise for diverse applications such as wearables, health monitors, and displays due to their cost-effective manufacturing methods. Despite the superior properties of metal oxides, the challenge of processing them at high temperatures incompatible with plastic substrates necessitates innovative annealing approaches. Photonic curing, which delivers microsecond to millisecond broadband (200–1500 nm) light pulses on a sample, emerges as a viable solution. Depending on the optical properties, the targeted film absorbs the radiant energy resulting in rapid heating while the transparent substrate absorbs a minimal amount of light and remains at ambient temperature. The light intensity can be high, but since the light pulse is short, the total energy absorbed by the sample remains low and will not damage the plastic substrate. This perspective explores the innovative application of photonic curing to fabricate flexible metal oxide optoelectronics, including thin-film transistors, metal–insulator–metal devices, solar cells, transparent conductors, and Li batteries, emphasizing the conversion of sol–gel precursors to metal oxides. However, this technique was initially developed for sintering metal nanoparticles to conductive patterns and poses intriguing challenges in explaining its mechanism for metal oxide conversion, especially considering the limited absorption of visible light by most sol–gel precursors. The review delves into UV-induced photochemistry, common flexible metal-oxide optoelectronic components, and non-intuitive distinctions between photonic curing and thermal annealing. By elucidating the distinctive role of photonic curing in overcoming temperature-related challenges and advancing the fabrication of flexible metal oxide optoelectronics, this perspective offers valuable insights that could shape the future of flexible optoelectronics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

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↗

Purification and identification of the fusicoccin binding protein from oat root plasma membrane

Fusicoccin (FC), a fungal phytotoxin, stimulates the H(+) -ATPase located in the plasma membrane (PM) of higher plants. The first event in the reaction chain leading to enhanced H(+) -efflux seems to be the binding of FC to a FC-binding protein (FCBP) in the PM. We solubilized 90% of the FCBP from oat (Avena sativa L. cv Victory) root PM in an active form with 1% octyl-glucoside. The FCBP was stabilized by the presence of protease inhibitors. The FCBP was purified by affinity chromatography using FC-linked adipic acid dihydrazide agarose (FC-AADA). Upon elution with 8 molar urea, two major protein bands on sodium dodecyl sulfate-polyaerylamide gel electrophoresis with molecular weights of 29,700 and 31,000 were obtained. Successive chromatography on BBAB Bio-Gel A, hexyl agarose, and FC-AADA resulted in the same two bands when the FC-AADA was eluted with sodium dodecyl sulfate. A direct correlation was made between 3H-FC-binding activity and the presence of the two protein bands. The stoichiometry of the 29,700 and 31,000 molecular weight bands was 1:2. This suggests that the FCBP occurs in the native form as a heterotrimer with an apparent molecular weight of approximately 92,000.

NASA Discipline Number 29-20↗