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At least 1,099 records · Page 61

Seeded emulsion polymerization as a powerful tool for the biofunctionalization of quantum dots

With the polymer encapsulation of quantum dots via seeded emulsion polymerization we present a powerful tool for the preparation of fluorescent nanoparticles with an extraordinary stability in aqueous solution. The method of the seeded emulsion polymerization allows a straightforward and simple in situ functionalization of the polymer shell under preserving the optical properties of the quantum dots. These requirements are inevitable for the application of semiconductor nanoparticles as markers for biomedical applications. Polymer encapsulated quantum dots have shown only a marginal loss of quantum yields when they were exposed to copper(II)-ions. Under normal conditions the quantum dots were totally quenched in presence of copper(II)-ions. Furthermore, a broad range of in situ functionalized polymer-coated quantum dots were obtained by addition of functional monomers or surfactants like fluorescent dye molecules, antibodies or specific DNA aptamers. Furthermore the emulsion polymerization can be used to prepare multifunctional hybrid systems, combining different nanoparticles within one construct without any adverse effect of the properties of the starting materials.{sup 1,2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An isolated water droplet in the aqueous solution of a supramolecular tetrahedral cage

Water under nanoconfinement at ambient conditions has exhibited low-dimensional ice formation and liquid–solid phase transitions, but with structural and dynamical signatures that map onto known regions of water’s phase diagram. Using terahertz (THz) absorption spectroscopy and ab initio molecular dynamics, we have investigated the ambient water confined in a supramolecular tetrahedral assembly, and determined that a dynamically distinct network of 9 ± 1 water molecules is present within the nanocavity of the host. The low-frequency absorption spectrum and theoretical analysis of the water in the Ga 4 L 6 12– host demonstrate that the structure and dynamics of the encapsulated droplet is distinct from any known phase of water. A further inference is that the release of the highly unusual encapsulated water droplet creates a strong thermodynamic driver for the high-affinity binding of guests in aqueous solution for the Ga 4 L 6 12– supramolecular construct.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid curing dynamics of PEG-thiol-ene resins allow facile 3D bioprinting and in-air cell-laden microgel fabrication

Thiol-norbornene photoclick hydrogels are highly efficient in tissue engineering applications due to their fast gelation, cytocompatibility, and tunability. In this work, we utilized the advantageous features of polyethylene glycol (PEG)-thiol-ene resins to enable fabrication of complex and heterogeneous tissue scaffolds using 3D bioprinting and in-air drop encapsulation techniques. We demonstrated that photoclickable PEG-thiol-ene resins could be tuned by varying the ratio of PEG-dithiol to PEG norbornene to generate a wide range of mechanical stiffness (0.5–12 kPa) and swelling ratios. Importantly, all formulations maintained a constant, rapid gelation time (<0.5 s). We used this resin in biological projection microstereolithography (BioPµSL) to print complex structures with geometric fidelity and demonstrated biocompatibility by printing cell-laden microgrids. Moreover, the rapid gelling kinetics of this resin permitted high-throughput fabrication of tunable, cell-laden microgels in air using a biological in-air drop encapsulation apparatus (BioIDEA). We demonstrated that these microgels could support cell viability and be assembled into a gradient structure. This PEG-thiol-ene resin, along with BioPµSL and BioIDEA technology, will allow rapid fabrication of complex and heterogeneous tissues that mimic native tissues with cellular and mechanical gradients. The engineered tissue scaffolds with a controlled microscale porosity could be utilized in applications including gradient tissue engineering, biosensing, and in vitro tissue models.

36 MATERIALS SCIENCE↗

Development of Cu(In,Ga)Se2 Test Coupons for Potential Induced Degradation Studies

We report on the design, fabrication and accelerated testing of fully encapsulated small area coupons (approximately 7.5cm x 7.5 cm) for the purpose of researching potential induced degradation in Cu(In, Ga)Se2 based PV modules. The fabrication of these coupons enables the study of the solar cells and the materials used in PV module manufacturing such as top and bottom glass covers of different composition (soda-lime glass, high temperature glass, alkaline-free glass, etc), plastic-based top covers, ethylene vinyl acetate and edge seal encapsulation materials. The coupons can also be used to emulate framed and frameless modules that utilize either monolithically interconnected modules or singular cell type of modules. The design of the coupons, their fabrication, the materials used and their testing for 1000 hours under 85 degrees C and 85% RH conditions are presented.

14 SOLAR ENERGY↗

Validation of Advanced Photovoltaic Module Materials and Processes by Combined-Accelerated Stress Testing (C-AST)

Tessolar module technology was developed to allow the incorporation of 5 incremental module material innovations. Combined, these innovations may improve the efficiency and durability of the standard silicon cell module. The innovations evaluated are: electrically conductive adhesive (ECA) replacing soldering of tabbing ribbons, light-capturing ribbon (LCR), silicone encapsulant, 2 mm front glass with backsheet, and a polymer-composite module frame. Tessolar-constructed individually encapsulated cells incorporating the material innovations are used to assemble 60-cell modules. 2 x 2 cell mini-modules of the same materials were produced for combined-accelerated stress testing (C-AST). C-AST results demonstrate that the 2 x 2 cell mini-module of Tessolar construction out-performed mini-modules using both ECA with EVA and standard solder with EVA constructions in power production over 108 cycles of testing.

14 SOLAR ENERGY↗

Interfacial Characterization of Positive Bias Voltage Degradation in PV Modules

Degradation from high system voltage is a prevailing failure mode in fielded photovoltaic modules, and the degradation mechanism is inherently dependent on the bias polarity. Here we report the effects of positive bias. Modules under positive bias demonstrated a significant photocurrent loss caused by two routes. First, delamination and discoloration of the silicon nitride layer, leading to optical loss determined by reflectance measurements. Second, chemical discoloration of the cell gridlines and encapsulant (EVA), which is linked to an electrochemical reaction at the silver electrodes. Chemical compositional analysis using X-ray photoemission spectroscopy demonstrated that the discoloration is attributed to Ag 2 S and/or Ag 2 O. Evidence of Ag ion migration from the cell grid into the encapsulant is observed after shallow depth profiling on the EVA surface. However, Ag was not detected at the EVA/glass interface, inferring limited Ag ion transport through the EVA. The source of sulfur is believed to be ambient air, which diffused into the module through the breathable backsheet.

characterization↗

Lessons from the IEC Durability of Adhesion Accelerated Test Sequence

The IEC 62788-1-1 and IEC 63209-2 standards use aging sequences for durability of adhesion in photovoltaic (PV) modules, which may be evaluated using the single cantilever beam (SCB) test. Because the encapsulant forms critical interfaces with the front glass and solar cells, degradation at those interfaces under ultraviolet (UV) exposure, elevated temperature, and humidity can lead to interfacial delamination - compromising the long-term reliability. In this work, adhesion durability of UV-transmitting poly(ethylene-co-vinyl acetate) (EVA) encapsulant to glass and to silicon solar cells is evaluated after sequenced UV and damp heat aging (85C/85%RH). Laminates were prepared using StarPhire solar front glass with thin glass or PERC cells, and two EVA formulations with different concentrations of siloxane coupling agent. Adhesion was quantified by measuring critical debond energy using the SCB method. Both formulations exhibit similar qualitative trends, while different adhesion is observed at the periphery despite the use of low-shrink manufacturing. The results show that while glass/EVA adhesion remains stable or increases after UV exposure and shows only moderate changes after damp heat, the EVA/cell interface exhibits an irreversible loss of adhesion following UV and then damp heat exposure. Although glass/EVA interfaces generally exhibit lower debond energies, the EVA/cell interface is significantly more vulnerable to UV-driven degradation, identifying it as the dominant reliability risk location through early- and intermediate-module life. These results demonstrate that accelerated aging sequences can expose large, interface-specific losses in adhesion durability and underscore the importance of interface engineering for long-term PV module reliability.

14 SOLAR ENERGY↗

Microencapsulation of Chemicals through Microfluidic-based Design and Fabrication

This presentation provides an overview of the polymer encapsulation program being conducted at LLNL in which a number of "active" materials (absorbents, catalysts, etc.) are being encapsulated in microfluidic capsule producing systems which produce particles that are solidified via UV radiation.

20 FOSSIL-FUELED POWER PLANTS↗

Validation of ORIGEN for VVER-440 Spent Fuel with Application to Fork Detector Safeguards Measurements

The US Department of Energy National Nuclear Security Administration and the European Atomic Energy Community (Euratom) are collaborating with the Radiation and Nuclear Safety Authority in Finland to assess spent fuel verification methods for potential application to measurements at the planned spent fuel encapsulation plant and geological repository prior to final disposal in Finland. The fork detector (FDET) used to measure the neutron and gamma radiation from a given spent fuel assembly is an existing technology widely used by the International Atomic Energy Agency (IAEA) and Euratom for the safeguards verification of spent fuel operator declaration. Recently, an FDET data analysis software, referred to as the ORIGEN module, was developed and incorporated into the IAEA/Euratom Integrated Review and Analysis Program. This module uses the ORIGEN burnup code to calculate the nuclide concentrations and the neutron and gamma source terms in the spent fuel based on operator declarations. Then, to predict the expected FDET signals for a given fuel assembly, the module combines the source terms calculated by ORIGEN with FDET response functions that were pre-generated using MCNP models. The inspector can compare the calculated signals to the measured values in real time to identify possible anomalies in fuel assembly’s operator declaration, integrity, or measurement. In this work, the capability of the ORIGEN module was extended from application to typical light water reactor fuels to use for VVER-440 assembly types. The accuracy of ORIGEN for this type of fuel assembly calculations was assessed by comparing calculated nuclide concentrations against destructive assay measurements for VVER-440 spent fuel. The performance of the ORIGEN module for FDET safeguards verification in routine inspections was assessed using FDET measurement data for 13 spent VVER-440 assemblies that were measured at the Loviisa Nuclear Power Plant in Finland, by comparing the calculated signals to the measured quantities. The results show that the calculated FDET neutron and gamma detector signals are generally within 12% of the measurements except for one assembly. Thus, these results are applicable to future safeguards verification in the planned Finland encapsulation plant, such as for passive neutron albedo reactivity safeguards measurements.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Waste Management Approach for a Potential Future U.S. Closed Fuel Cycle - 16233

The U.S. Department of Energy, Office of Nuclear Energy has chartered an effort to develop technologies to enable safe and cost effective recycle of commercial used nuclear fuel (UNF) in the U.S. Part of this effort includes the evaluation of exiting waste management technologies for effective treatment of wastes in the context of current U.S. regulations and development of waste forms and processes with significant cost and/or performance benefits over those existing. This study summarizes the results of these ongoing efforts with a focus on the highly radioactive primary waste streams. The primary streams considered and the recommended waste forms include: - Tritium separated from either a low volume gas stream or a high volume water stream. The recommended waste form is low-water cement in high integrity containers. - Iodine-129 separated from off-gas streams in aqueous processing. There are a range of potentially suitable waste forms. As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals. - Carbon-14 separated from LWR fuel treatment off-gases and immobilized as a CaCO{sub 3} in a cement waste form. - Krypton-85 separated from LWR and SFR fuel treatment off-gases and stored as a compressed gas. - An aqueous reprocessing high-level waste (HLW) raffinate waste which is immobilized by the vitrification process in one of three forms: a single phase borosilicate glass, a borosilicate based glass ceramic, or a multi-phased titanate ceramic [e.g., synthetic rock (Synroc)]. - An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel that is either included in the borosilicate HLW glass or is immobilized in the form of a metal alloy in the case of glass ceramics or titanate ceramics. - Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware that are washed and super-compacted for disposal or as an alternative Zr purification and reuse (or disposal as low-level waste, LLW) by reactive gas separations. - Electrochemical process salt HLW which is immobilized in a glass bonded Sodalite waste form known as the ceramic waste form (CWF). - Electrochemical process UDS and SS cladding hulls which are melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Large Cask, Small Building, AREVA's Safe MLLW Disposal Solution Despite Facility Limitations - 16295

In order to begin decommissioning of a 1950's research reactor, Class C Mixed Low Level Waste (MLLW) had to be removed from the facility and disposed of. The AREVA TN RAM cask, designed and licensed for shipping Type B waste packages, was chosen as the most appropriate shipping solution. Due to the building layout, crane capacity and pool size, the standard TN RAM cask loading process could not be utilized. Unique solutions and approaches had to be developed to complete the project. AREVA designed a smaller liner insert that would house the four MLLW components in a single waste package to solve the problems related to crane capacity and physical pool dimensions. AREVA also designed and fabricated a shield bell to provide radiation shielding while moving the liner insert from the reactor pool to the cask that was staged adjacent to the reactor pool. The AREVA team worked with the disposal facility to cover requirements for disposal of Class B MLLW. This included designing spacers filled with inert material to fulfill the requirement for maximum 10% void space in the waste package. This disposal method for Class C waste met the requirements of macro-encapsulation. Therefore, no additional treatment action was required when disposing of Class C MLLW. AREVA's solution provides a model for disposing MLLW requiring macro-encapsulation in a single waste package. This solution also provides a model for how to adapt large shipping casks and liners to smaller aging commercial, DOE or research facilities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Small Waste in a Large Package - Meeting Requirements for Packaging, Transport and Disposal - 18092

A small amount of Class C Mixed Low Level Waste (MLLW) required packaging and disposition to an off-site facility. The AREVA TN RAM cask, designed and licensed for shipping Type B waste packages, was chosen as the most appropriate shipping solution. Due to packaging, shipping and disposal requirements, the standard TN RAM cask could not be utilized without making some modifications. Unique solutions and approaches had to be developed by the AREVA design team to complete the project within the anticipated budget and schedule. The general work scope was to characterize, remove from a pool, profile, package, certify and transport four irradiated components to an approved off-site facility. The material makeup of the components (three stainless steel plates and a lead counterweight) resulted in a MLLW classification which required special packaging and disposal methods. The AREVA design team worked with the disposal facility to identify all requirements associated with disposal of Class B/C MLLW. After defining the packaging and disposal requirements, it was determined that unique spacers and void fillers would be required. The design solution consisted of a liner insert as well as axial and radial spacers filled with inert material. Remaining voids in the liner insert were filled with recycled glass beads to fulfill the requirement for maximum 10% void space in the waste package. The axial spacers also served to center the waste load in the shipping cask to comply with the AREVA TN RAM Cask NRC license. Concentration averaging and waste consolidation were used to reach the Class C MLLW determination for shipping and disposal. This disposal method for Class C waste met the requirements of macro-encapsulation. Therefore, no additional treatment action was required when disposing of Class C MLLW. AREVA's solution provides a model for meeting macro-encapsulation requirements while also meeting void space requirements. This solution provides a model for how to adapt large shipping casks and liners to smaller waste packages that would not normally be a good fit for traditional casks. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Use of Geopolymers to Immobilise Sellafield Historic, Intermediate Level Wastes - 19547

A number of geopolymer formulations have been investigated for application to Sellafield ILWs, from sludges to solid items. Trials using Magnox sludge and clinoptilolite simulants have demonstrated that higher incorporation rates of simulated wastes are possible when using a geopolymer, compared to traditional OPC based cement formulations. Trials on scaled zeolite packages, containing simulated AW500 zeolite, have indicated that encapsulation with geopolymers are possible, with mild agitation. This has been possible even when left fully saturated with over standing water and provides a simple method to immobilize ion exchange materials inside sealed containers. The base geopolymers and encapsulated products have been characterised for viscosity, leach rate, physical properties, gas permeability and resistance to radiation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solidification of Low and Intermediate Level Waste - A Comparison between Different Methods - 19584

The treatment of radioactive materials results in products that have to be suitable for a period of interim storage as well as for disposal in a repository. Considering available options for treatment of radioactive waste, future disposal also has to be taken into account. Up to now, only cementation and encapsulation in geopolymer (only to limited extent) are relevant treatment methods for the solidification of German waste for disposal in the repository Grube Konrad. However, a synopsis of other solidification technologies is considered to be helpful in order to be prepared for future developments in the fields of radioactive waste treatment. Treatment methods addressed in this paper are: - Cementation; - Encapsulation into geopolymer matrix; - Vitrification; - SYNROC; - Geomelting. The criteria for evaluation of the treatment methods are as follows: - Requirements concerning waste properties; - Safety of treatment facilities; - Fulfillment of waste acceptance criteria for repository Grube Konrad; - Fulfillment of requirements for near surface disposal; - Suitability for long-term interim storage. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Focused Helium Ion Beam for Direct Patterning of Monolayer MoS 2 Nanoribbon Field Effect Devices

The helium ion microscope (HIM) focused ion beam (FIB) has emerged as a powerful tool to directly pattern nanostructures below 10 nm due to its high-resolution capabilities and the inert nature of the ion source. These attributes make HIM FIB particularly interesting for patterning 2D materials such as transition metal dichalcogenides (TMDs) to investigate transport phenomena at the nanoscale. Reported here is the fabrication of MoS 2 nanoribbon devices using HIM FIB-induced etching (FIBIE) with XeF 2 , allowing for reduced ion dose compared to direct sputtering. While patterning is efficacious, the devices exhibit performance degradation with decreasing nanoribbon width due to damage up to 150 nm beyond the patterned edge. Incorporating an hBN encapsulation improves device performance by one order of magnitude, although the lateral extent of damage remains unchanged. The spatial distribution of damage is shown to be determined by the forward- and backscattered ions and electrons, while the hBN encapsulation layer substantially reduces damage from XeF 2 interactions in unexposed regions. Raman and photoluminescence (PL) measurements corroborate these findings, while ion/solid interaction simulations further elucidate the resolution limits imposed by substrate interactions. In conclusion, this work provides critical insights and a practical pathway for utilizing HIM FIBIE in 2D TMD functional device patterning.

MoS 2↗

Free-Standing Bialkali Photocathodes Using Atomically Thin Substrates

This study reports successful deposition of high quantum efficiency (QE) bialkali antimonide K2CsSb photocathodes on graphene films. The results pave the way for an ultimate goal of encapsulating technologically relevant photocathodes for accelerator technology with an atomically thin protecting layer to enhance lifetime while minimizing QE losses. A QE of 17% at approximate to 3.1 eV (405 nm) is the highest value reported so far on graphene substrates and is comparable to that obtained on stainless steel and nickel reference substrates. The spectral responses of the photocathodes on graphene exhibit signature features of K2CsSb including the characteristic absorption at approximate to 2.5 eV. Materials characterization based on X-ray fluorescence and X-ray diffraction reveals that the composition and crystal quality of these photocathodes deposited on graphene is comparable to those deposited on a reference substrate. Quantitative agreement between optical calculations and QE measurements for the K2CsSb on free suspended graphene and a graphene-coated metal substrate further confirms the high-quality interface between the photocathodes and graphene. Finally, a correlation between the QE and graphene quality as characterized by Raman spectroscopy suggests that a lower density of atomistic defects in the graphene films leads to higher QE of the deposited K2CsSb photocathodes.

accelerator technology↗

Restriction-In-Motion of Surface Ligands Enhances Photoluminescence of Quantum Dots - Experiment and Theory

Here the relationship between emission and ligand restriction of a series of ZnSe/ZnS quantum dots (QDs) encapsulated in nanoparticles is investigated systematically via experiments and quantum theory. The QDs have a ZnSe core and a ZnS shell, capped with hydrophobic ligands (triotylphosphine oxide/hexadecylamine), allowing them to be entrapped in a model biomembrane, bicelle, made of zwitterionic dipalmitoyl and dihexanoyl phosphatidylcholines and charged dipalmitoyl phosphatidylglycerol. Enhanced photoluminescence is observed upon encapsulation, depending on the QD-to-lipid ratio. Transmission electron microscopy and small-angle X-ray scattering confirm that QDs are preferably situated at the rim of bicellar discs. A simplified quantum dissipation heat-bath theory is proposed to correlate the enhancement with slower nonradiative processes caused by the restriction-in-motion (RIM) of the surface ligands. However, Fõrster resonance energy transfer due to QD aggregation counteracts the effect.

36 MATERIALS SCIENCE↗

Catalytically Active Site Mapping Realized through Energy Transfer Modeling

Abstract The demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host–guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal–organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO 2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host–guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host–guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.

Thompson, William J.↗