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At least 181 records · Page 10

High energy density picoliter-scale zinc-air microbatteries for colloidal robotics

The recent interest in microscopic autonomous systems, including microrobots, colloidal state machines, and smart dust, has created a need for microscale energy storage and harvesting. However, macroscopic materials for energy storage have noted incompatibilities with microfabrication techniques, creating substantial challenges to realizing microscale energy systems. Here, we photolithographically patterned a microscale zinc/platinum/SU-8 system to generate the highest energy density microbattery at the picoliter (10 −12 liter) scale. The device scavenges ambient or solution-dissolved oxygen for a zinc oxidation reaction, achieving an energy density ranging from 760 to 1070 watt-hours per liter at scales below 100 micrometers lateral and 2 micrometers thickness in size. The parallel nature of photolithography processes allows 10,000 devices per wafer to be released into solution as colloids with energy stored on board. Within a volume of only 2 picoliters each, these primary microbatteries can deliver open circuit voltages of 1.05 ± 0.12 volts, with total energies ranging from 5.5 ± 0.3 to 7.7 ± 1.0 microjoules and a maximum power near 2.7 nanowatts. We demonstrated that such systems can reliably power a micrometer-sized memristor circuit, providing access to nonvolatile memory. We also cycled power to drive the reversible bending of microscale bimorph actuators at 0.05 hertz for mechanical functions of colloidal robots. Additional capabilities, such as powering two distinct nanosensor types and a clock circuit, were also demonstrated. The high energy density, low volume, and simple configuration promise the mass fabrication and adoption of such picoliter zinc-air batteries for micrometer-scale, colloidal robotics with autonomous functions.

Robotics↗

Photoinduced Degradation of the Optical Properties of Colloidal Ag{sub 2}S and CdS Quantum Dots Passivated by Thioglycolic Acid

The results of studying degradation of the optical properties of colloidal Ag{sub 2}S and CdS quantum dots (QDs) 2.6–3.2 nm in size passivated by thioglycolic acid (TGA) are presented. The photoluminescence intensity of colloidal Ag{sub 2}S QDs has been found to decrease under laser irradiation at a wavelength of 445 nm, beginning with the effective power of 10 mW. The observed effect is interpreted as a photochemical reaction of formation of new nonradiative-recombination channels in Ag{sub 2}S QDs upon excitation. It is established for colloidal CdS QDs passivated by TGA that a decrease in the optical density in the entire absorption spectrum and the luminescence intensity is accompanied by precipitation of the colloidal particles in a cell and related to photodegradation of the passivating shell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Colloid-Facilitated Radionuclide Transport: Current State of Knowledge from a Nuclear Waste Repository Risk Assessment Perspective

This report provides an overview of the current state of knowledge of colloid-facilitated radionuclide transport from a nuclear waste repository risk assessment perspective. It draws on work that has been conducted over the past 3 decades, although there is considerable emphasis given to work that has been performed over the past 3-5 years as part of the DOE Used Fuel Disposition Campaign. The timing of this report coincides with the completion of a 3-year DOE membership in the Colloids Formation and Migration (CFM) partnership, an international collaboration of scientists studying colloid-facilitated transport of radionuclides at both the laboratory and field-scales in a fractured crystalline granodiorite at the Grimsel Test Site in Switzerland. This Underground Research Laboratory has hosted the most extensive and carefully-controlled set of colloid-facilitated solute transport experiments that have ever been conducted in an in-situ setting, and a summary of the results to date from these efforts, as they relate to transport over long time and distance scales, is provided in Chapter 3 of this report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The impacts of pore-scale physical and chemical heterogeneities on the transport of radionuclide-carrying colloids

Independent of the methods of nuclear waste disposal, the degradation of packaging materials could lead to mobilization and transport of radionuclides into the geosphere. This process can be significantly accelerated due to the association of radionuclides with the backfill materials or mobile colloids in groundwater. The transport of these colloids is complicated by the inherent coupling of physical and chemical heterogeneities (e.g., pore space geometry, grain size, charge heterogeneity, and surface hydrophobicity) in natural porous media that can exist on the length scale of a few grains. In addition, natural colloids themselves are often heterogeneous in their surface properties (e.g., clay platelets possess opposite charges on the surface and along the rim). Both physical and chemical heterogeneities influence the transport and retention of radionuclides under various groundwater conditions. However, the precise mechanisms how these coupled heterogeneities influence colloidal transport are largely elusive. This knowledge gap is a major source of uncertainty in developing accurate models to represent the transport process and to predict distribution of radionuclides in the geosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Actinide (III/IV) - Silica Colloids in the WIPP

During the completeness process for the 2019 Compliance Recertification Application (CRA) for the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) raised concerns about the possible presence of actinide-silica colloids in the WIPP. Several publications that studied the An(IV)- silica system indicated that these colloids could form under conditions similar to WIPP. Colloids are important for WIPP Performance Assessment (PA) as these are a mobile fraction of actinides that contribute to release. As the previously published papers did not explore the formation of actinide-silica colloids under the high ionic strength environment expected in WIPP, an experimental strategy to study these systems was developed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Crystalline Colloidal Arrays in Polymer Matrices

Crystalline Colloidal Arrays (CCA, also known as colloidal crystals), composed of aqueous or nonaqueous dispersions of self-assembled nanosized polymer colloidal spheres, are emerging toward the development of advanced optical devices for technological applications. The spontaneous self assembly of polymer spheres in a dielectric medium results from the electrostatic repulsive interaction between particles of uniform size and charge distribution. In a way similar to atomic crystals that diffract X-rays, CCA dispersions in thin quartz cells selectively and efficiently Bragg diffract the incident visible light. The reason for this diffraction is because the lattice (body or face centered cubic) spacing is on the order of the wavelength of visible light. Unlike the atomic crystals that diffract a fixed wavelength, colloidal crystals in principle, depending on the particle size, particle number and charge density, can diffract W, Vis or IR light. Therefore, the CCA dispersions can be used as laser filters. Besides, the diffraction intensity depends on the refractive index mismatch between polymer spheres and dielectric medium; therefore, it is possible to modulate incident light intensities by manipulating the index of either the spheres or the medium. Our interest in CCA is in the fabrication of all-optical devices such as optical switches, limiters, and spatial light modulators for optical signal processing. The two major requirements from a materials standpoint are the incorporation of suitable nonlinear optical materials (NLO) into polymer spheres which will allow us to alter the refractive index of the spheres by intense laser radiation, and preparation of solid CCA filters which can resist laser damage. The fabrication of solid composite filters not only has the advantage that the films are easier to handle, but also the arrays in solid films are more robust than in liquid media. In this paper, we report the photopolymerization process used to trap CCA in polymer matrices, the factors which affect the optical diffraction qualities of resulting polymer films, and methods to improve the efficiencies of solid optical filters. Before this, we also present the experimental demonstration, of controlling the optical diffraction intensities from aqueous CCA dispersions by varying the temperature, which establishes the feasibility of fabricating all-optical switching devices with nonlinear periodic array structures.

Sunkara, Hari B.↗

Physics of Colloids in Space (PCS) Flight Hardware Developed

investigation that will be located in an Expedite the Process of Experiments to Space Station (EXPRESS) Rack. The investigation will be conducted in the International Space Station U.S. laboratory, Destiny, over a period of approximately 10 months during the station assembly period from flight 6A through flight UF-2. This experiment will gather data on the basic physical properties of colloids by studying three different colloid systems with the objective of understanding how they grow and what structures they form. A colloidal suspension consists of fine particles (micrometer to submicrometer) suspended in a fluid for example, paints, milk, salad dressings, and aerosols. The long-term goal of this investigation is to learn how to steer the growth of colloidal suspensions to create new materials and new structures. This experiment is part of a two-stage investigation conceived by Professor David Weitz of Harvard University along with Professor Peter Pusey of the University of Edinburgh. The experiment hardware was developed by the NASA Glenn Research Center through contracts with Dynacs, Inc., and ZIN Technologies.

Koudelka, John M.↗

Using colloidal silica as isolator, diverter and blocking agent for subsurface geological applications

A system for blocking fast flow paths in geological formations includes preparing a solution of colloidal silica having a nonviscous phase and a solid gel phase. The solution of colloidal silica is injected into the geological formations while the solution of colloidal silica is in the nonviscous phase. The solution of colloidal silica is directed into the fast flow paths and reaches the solid gel phase in the fast flow paths thereby blocking flow of fluid in the fast paths.

58 GEOSCIENCES↗

Using colloidal silica as a zonal isolation material and fast path blocker in geological formations

A system for blocking fast flow paths in geological formations includes preparing a solution of colloidal silica having a nonviscous phase and a solid gel phase. The solution of colloidal silica is injected into the geological formations while the solution of colloidal silica is in the nonviscous phase. The solution of colloidal silica is directed into the fast flow paths and reaches the solid gel phase in the fast flow paths thereby blocking flow of fluid in the fast paths.

02 PETROLEUM↗

Solution‐Processed Spin‐Polarized Light‐Emitting Diodes of Colloidal Quantum Wells and Magnetic Nanoparticles

Electrical injection of spin-polarized carriers into semiconductors enables circularly-polarized emission from spin-polarized light-emitting diodes (spin-LEDs). The incredible level of tunability of magnetic and electronic properties in colloidal nanocrystals offers unprecedented opportunities for the modulation of polarization of light in solution-processed spin-LEDs based on magnetic nanoparticles unlike epitaxially grown spin-LEDs restricted by a very limited range of materials for their exploitation, and solution-processed spin-LEDs based on chiral molecules, which do not allow the modulation of polarization in general. Here, it is shown that electrical injection of spin-polarized electrons from magnetic Fe 3 O 4 nanoparticles into CdSe/CdZnS core/shell colloidal quantum wells (CQWs) in solution-processed LEDs that allows for polarization modulation of electroluminescence. In this structure, a monolayer of face-down oriented CQWs is deposited as an active layer to avoid polarization losses due to the hopping of the electrons between the CQWs before the radiative recombination process. In this solution-processed spin-LED, the circular polarization reaches 4.5% at 3 K and survives up to 100 K. A net circular polarization is observed at zero magnetic field up to 100 K because of the remnant magnetization of the Fe 3 O 4 nanoparticles. This new colloidal spin-LED architecture presents significant prospects for future solution-processed advanced opto-spintronic devices.

circularly polarized electroluminescence↗

Microdynamics of active particles in defect-rich colloidal crystals

Hypothesis. Because they are self-propulsive, active colloidal particles can interact with their environment in ways that differ from passive, Brownian particles. Here, we explore how interactions in different microstructural regions may contribute to colloidal crystal annealing. Experiments. We investigate active particles propagating in a quasi-2D colloidal crystal monolayer produced by alternating current electric fields (active-to-passive particle ratio ~ 1:720). The active particle is a platinum Janus sphere propelled by asymmetric decomposition of hydrogen peroxide. Crystals are characterized for changes in void properties. The mean-squared-displacement of Janus particles are measured to determine how active microdynamics depend on the local microstructure, which is comprised of void regions, void-adjacent regions (defined as within three particle diameters of a void), and interstitial regions. Findings. At active particle energy E A = 2.55 k B T, the average void size increases as much as three times and the average void anisotropy increases about 40% relative to the passive case. Further, the average microdynamical enhancement, <δ(t)>, of Janus particles in the crystal relative to an equivalent passive Janus particle is reduced compared to that of a free, active particle (<δ(t) > is 1.88 ± 0.04 and 2.66 ± 0.08, respectively). The concentration of active particles is enriched in void and void-adjacent regions. Active particles exhibit the greatest change in dynamics relative to the passive control in void-adjacent regions (<δ(t)> = 2.58 ± 0.06). The results support the conjecture that active particle microdynamical enhancement in crystal lattices is affected by local defect structure.

36 MATERIALS SCIENCE↗

Colloidal Stability of PFSA-Ionomer Dispersions. Part I. Single-Ion Electrostatic Interaction Potential Energies

Charged colloidal particles neutralized by a single counterion are increasingly important for many emerging technologies. Attention here is paid specifically to hydrogen fuel cells and water electrolyzers whose catalyst layers are manufactured from a perfluorinated sulfonic acid polymer (PFSA) suspended in aqueous/alcohol solutions. Partially dissolved PFSA aggregates, known collectively as ionomers, are stabilized by the electrostatic repulsion of overlapping diffuse double layers consisting of only protons dissociated from the suspended polymer. We denote such double layers containing no added electrolyte as "single ion". Size-distribution predictions build upon interparticle interaction potential energies from the Derjaguin-Landau-Verwey-Overbeek (DLVO) formalism. However, when only a single counterion is present in solution, classical DLVO electrostatic potential energies no longer apply. Accordingly, here a new formulation is proposed to describe how single-counterion diffuse double layers interact in colloidal suspensions. Part II (Srivastav, H.; Weber, A. Z.; Radke, C. J. Langmuir 2024 DOI: 10.1021/acs.langmuir.3c03904) of this contribution uses the new single-ion interaction energies to predict aggregated size distributions and the resulting solution pH of PFSA in mixtures of n-propanol and water. A single-counterion diffuse layer cannot reach an electrically neutral concentration far from a charged particle. Consequently, nowhere in the dispersion is the solvent neutral, and the diffuse layer emanating from one particle always experiences the presence of other particles (or walls). Thus, in addition to an intervening interparticle repulsive force, a backside osmotic force is always present. With this new construction, we establish that single-ion repulsive pair interaction energies are much larger than those of classical DLVO electrostatic potentials. The proposed single-ion electrostatic pair potential governs dramatic new dispersion behavior, including dispersions that are stable at a low volume fraction but unstable at a high volume fraction and finite volume-fraction dispersions that are unstable with fine particles but stable with coarse particles. Finally, the proposed single-counterion electrostatic pair potential provides a general expression for predicting colloidal behavior for any charged particle dispersion in ionizing solvents with no added electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Near-Field Nanoimaging of Colloidal Transition Metal Dichalcogenide Waveguides

Bulk transition metal dichalcogenide (TMDC) nanostructures are regarded as promising material candidates for integrated photonics due to their high refractive index at the near-infrared wavelengths. Here in this work, colloidal TMDC waveguides with tailorable dimensions are prepared by a scalable synthetic approach. The optical waveguiding properties of colloidal nanowires are studied by the near-field nanoimaging technique. In addition to dependence on thickness and wavelength, the excitonic responses and resultant waveguide modes in TMDC nanowires can be modulated by the environmental temperature. With the high-throughput production and tunable optical properties, colloidal TMDC nanowires highlight the potential for active optical components and integrated photonic devices.

36 MATERIALS SCIENCE↗

New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica

A highly modular synthesis of designed catalysts with controlled bimetallic nanoparticle size and composition and a well-defined structural hierarchy is shown. Exemplary catalysts—bimetallic dilute Ag-in-Au nanoparticles partially embedded in a porous SiO 2 matrix (SiO 2 –Ag x Au y )—were synthesized by the decoration of polymeric colloids with the bimetallic nanoparticles followed by assembly into a colloidal crystal backfilled with the matrix precursor and subsequent removal of the polymeric template. This work reports that these new catalyst architectures are significantly better than nanoporous dilute AgAu alloy catalysts (nanoporous Ag 3 Au 97 ) while retaining a clear predictive relationship between their surface reactivity with that of single-crystal Au surfaces. This paves the way for broadening the range of new catalyst architectures required for translating the designed principles developed under controlled conditions to designed catalysts under operating conditions for highly selective coupling of alcohols to form esters. Excellent catalytic performance of the porous SiO 2 –Ag x Au y structure for selective oxidation of both methanol and ethanol to produce esters with high conversion efficiency, selectivity, and stability was demonstrated, illustrating the ability to translate design principles developed for support-free materials to the colloid-templated structures. The synthetic methodology reported is customizable for the design of a wide range of robust catalytic systems inspired by design principles derived from model studies. Fine control over the composition, morphology, size, distribution, and availability of the supported nanoparticles was discussed.

36 MATERIALS SCIENCE↗

Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. Here, we have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ~80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of highly carboxylated colloidal polymers on cement hydration and interactions with calcium ions

Polymer latexes are often found to retard cement hydration. Interaction of polymer particles with Ca{sup 2+} in pore solution and adsorption of polymer on cement were proposed as possible mechanisms for the retardation effect. This paper aims at disclosing the retardation mechanism of colloidal polymers using a highly carboxylated polystyrene latex. Interaction between colloidal particles and Ca{sup 2+} was studied by post-treatment of the latex with Ca(NO{sub 3}){sub 2}. Techniques including calorimetry, adsorption test, ICP-OES, SEM, are involved to investigate effects of the post-treated latexes on hydrations of cement and C{sub 3}S. It is found that enrichment of Ca{sup 2+} on surface of colloidal particles doesn't contribute to the retardation effect of polymer on cement hydration. Furthermore, the acceleration effect of the two-step treated latex using Ca(NO{sub 3}){sub 2} and Na{sub 2}SiO{sub 3} suggests that nucleation inhibition of the adsorbed polymer layer on cement surface is the more conceivable mechanism responsible for the retardation effect of the highly carboxylated latex.

36 MATERIALS SCIENCE↗

Reconfigurable self-assembly of porous anisotropic colloids in nematic liquid crystals

Dispersions of anisotropic nanoparticles in liquid crystalline hosts recently yielded new soft condensed matter states, like the thermally reconfigurable monoclinic and orthorhombic biaxial nematic liquid crystals, with a plethora of unusual phases and phase transformations. Our current study shows that the nanoscale porous nature of colloids with micrometer-range overall dimensions also enables highly reconfigurable orientations and assemblies of the microparticles, allowing for realization of condensed matter states with unusual combinations of low-symmetry nematic or smectic order and fluidity. Much like the anisotropic nanoparticles studied previously, these nanoporous anisotropic colloids exhibit thermally reconfigurable oriented alignment with respect to the far-field director, as well as diverse low-symmetry liquid crystalline phase behaviors. Furthermore, our findings open doors to fundamental and applied uses of low-symmetry molecular-colloidal orientationally ordered states of matter with uninhibited fluidity, as well as liquid crystals with partial positional ordering, like low-symmetry smectics, which could lead to applications in metamaterial designs, electro-optics, photonics, etc.

colloidal dispersion↗

In situ probing of structure and deagglomeration of SnO 2 colloids via small-angle X-ray scattering

Transforming dry nanopowders into stable colloidal dispersions remains challenging due to the cohesive forces between the nanoparticles (NPs) which promote agglomeration. Effective dispersion and deagglomeration of these agglomerates is a critical process in the formulation and preparation of nanoparticle-based functional materials via the colloidal route. Understanding the deagglomeration dynamics provides information to improve microstructural quality in various applications by enabling engineering of agglomerate size, structure and morphology. However, the deagglomeration process dynamics with respect to the evolution of the fractal agglomerate structures, particularly for very small NPs, is still poorly understood and requires further investigation. This study employs in situ small-angle X-ray scattering (SAXS) to investigate the sonication-induced deagglomeration of SnO 2 NPs. Electrostatically stabilized SnO 2 colloids with varying primary particle size (6–21 nm) are investigated in a specifically designed in situ cell using synchrotron-based SAXS to study the influence of sonication time and intensity on the nanoscaled agglomerates. Complete structural analysis via SAXS reveals a direct correlation between changes in agglomerate size and structure, size-dependent deagglomeration behavior and a dependence on the overall energy introduced during sonication into the dispersion regardless of the actual power as well as ultrasonic process parameters in case of SnO 2 NPs. The results suggest that control of the dispersion process during ultrasonic deagglomeration results in tailoring agglomerates with respect to size and structure.

Deagglomeration↗