Movement with light: Photoresponsive shape morphing of printed liquid crystal elastomers
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The behavior of fluids at supercritical thermodynamic conditions is inherently complex due to large variations in thermodynamic and transport properties. Recent numerical and experimental investigations illustrate ongoing interest for these fluids, especially supercritical CO 2 and supercritical water, for a variety of applications. For example, supercritical water reactors (SCWR) operate in this extreme condition of high-pressure and temperature, resulting in highly dynamic flow fields and unexpected heat transfer regimes. The potential heat transfer benefits in this regime are directly associated with the extreme variations in thermodynamic and transport properties, which occur at, and above, the critical point. This work characterizes the hydrodynamic instabilities that arise for fluids at supercritical thermodynamic conditions when buoyancy forces are significant. Two specific configurations are considered, a natural convection cavity flow, and a mixed convection, heated, horizontal channel flow. Natural convection flow in a cavity is a classical configuration with expected behavior below the critical point. This configuration aids in characterizing the effect of the variable properties in the supercritical thermodynamic regime. Further, limited studies in the existing literature have been conducted for low-Reynolds and intermediate-Rayleigh numbers, mixed-convection channel flows for supercritical water, which is the focus of the channel flow configuration. To investigate the thermally driven hydrodynamic instabilities in this regime, a high-order fully-implicit numerical method is used. Such strong variations in thermophysical properties (in particular, density) are difficult to simulate and an altogether compressible framework is needed. Therefore, the compressible Navier-Stokes equations are solved without any additional assumptions. The fully implicit, high-order in space and time, reconstructed discontinuous Galerkin method as implemented within the multi-physics code called ALE3D (Arbitrary Lagrangian and Eulerian in 2D and 3D), developed at Lawrence Livermore National Laboratory (LLNL), is used. This fully implicit, L-stable method accurately captures the compressible nature of the ow in the limit of very low Mach number. It has been widely accepted that above the critical point, only one phase is observed. However, recent research has indicated the existence of the distinct gas-like and liquid-like regions separated by the Widom line, the locus of the maxima of the specific heat. Along the Widom line, density decreases 6-fold, viscosity drops by a factor of 2, while specific heat spikes by an order of magnitude. These variations, specifically in density and viscosity, produce a thick pseudo-interface and flow dynamics behavior akin to film boiling. A pseudo-film at the heated wall of the cavity and the horizontal channel is observed where buoyancy forces induce mixing through the specific configurations. Further the local Rayleigh and Richardson numbers provide maps of the flow field and the buoyancy forces driving the microscopic mixing. In the first chapter, I describe a background of supercritical fluid and the various applications. The second chapter focuses on the mathematical model and numerical method used for simulations, where a description of the equation of state for supercritical water is described. The third chapter focuses on the natural convection cavity with a heated bottom wall. In this cavity a gas-like and a liquid-like flow within the supercritical thermodynamic regime are observed. The fourth chapter focuses on a forced convection, horizontal channel, distinguishing between the gas-like, liquid-like, and mixed flow regimes. Mixed convection flow, with the addition of gravitational forces in the horizontal channel show the influence of variable properties on the hydrodynamic development, heat transfer, and rising instabilities. The last chapter of this research focuses on characterizing the unstable hydrodynamics through time-averaging processes and analysis of the movement of energy through the developing plumes.
Here, in this study, based on a small-scale quench test facility, the two-phase flow interface behavior during quench transients is visualized and analyzed utilizing an image processing framework. The high-fidelity experimental results obtained for two-phase flow in the current framework can support various studies both in the time domain and in the frequency domain. In particular, visualization of the data obtained from different heating surfaces under different test conditions are used to perform a full-scale transient 2-D vapor film reconstruction. The liquid-vapor interface variations in various heat transfer regimes as well as at the initial film breakup point can be directly obtained through the processed data. Moreover, the temporal variation of the interfacial wave frequency approaching quench is investigated in detail. Based on the high-resolution data obtained for the liquid-vapor interface, the detailed phase velocity and temperature profiles are obtained through theoretic analysis, based on which the film boiling heat transfer coefficient (HTC) can be determined. In addition, an improved film boiling HTC model is developed considering the effects of wall superheat, liquid subcooling temperature, vapor film thickness as well as fluid properties. The model is found to predict film boiling HTC well within 15% error.
After completion of LHC Run 2, the ATLAS and CMS experiments had collected of order 139 fb –1 of data at √s = 13 TeV. While discovering a very Standard Model-like Higgs boson of mass m h ≃ 125 GeV, no solid signal for physics beyond the Standard Model has emerged so far at LHC. In addition, no WIMP signals have emerged so far at ton-scale noble liquid WIMP search experiments. For the case of weak scale supersymmetry (SUSY), which is touted as a simple and elegant solution to the gauge hierarchy problem and likely low energy limit of compactified string theory, LHC has found rather generally that gluinos are beyond about 2.2 TeV whilst top squark must lie beyond 1.1 TeV. These limits contradict older simplistic notions of naturalness that emerged in the 1980s–1990s, leading to the rather pessimistic view that SUSY is now excluded except for perhaps some remaining narrow corners of parameter space. Yet, this picture ignores several important developments in SUSY/string theory that emerged in the 21st century: 1. the emergence of the string theory landscape and its solution to the cosmological constant problem, 2. a more nuanced view of naturalness including the notion of “stringy naturalness”, 3. the emergence of anomaly-free discrete R-symmetries and their connection to R-parity, Peccei-Quinn symmetry, the SUSY μ problem and proton decay and 4. the importance of including a solution to the strong CP problem. Rather general considerations from the string theory landscape favor large values of soft terms, subject to the vacuum selection criteria that electroweak symmetry is properly broken (no charge and/or color breaking (CCB) minima) and the resulting magnitude of the weak scale is not too far from our measured value. Then stringy naturalness predicts a Higgs mass m h ~ 125 GeV whilst sparticle masses are typically lifted beyond present LHC bounds. Lastly, in light of these refinements in theory perspective confronted by LHC and dark matter search results, we review the most likely LHC, ILC and dark matter signatures that are expected to arise from weak scale SUSY as we understand it today.
Liquid argon detectors are employed in a wide variety of nuclear and particle physics experiments. The addition of small quantities of xenon to argon modifies its scintillation, ionization, and electroluminescence properties and can improve its performance as a detection medium. However, a liquid argon-xenon mixture can develop instabilities, especially in systems that require phase transitions or that utilize high xenon concentrations. In this work, we analyze the causes of these instabilities and describe a small (liter-scale) apparatus with a unique cryogenic circuit specifically designed to handle argon-xenon mixtures. The system is capable of condensing argon gas mixed with $\mathscr{O}$ (1%) xenon by volume and maintains a stable liquid mixture near the xenon saturation limit while actively circulating it in the gas phase. We also demonstrate control over instabilities that develop when the detector condition is allowed to deviate from optimized settings. This progress enables future liquid argon detectors to benefit from the effects of high concentrations of xenon doping, such as more efficient detection of low-energy ionization signals. In conclusion, this work also develops tools to study and mitigate instabilities in large argon detectors that use low concentration xenon doping.
The two-channel Kondo lattice likely hosts a rich array of phases, including hastatic order, a channel symmetry breaking heavy Fermi liquid. In this work, we revisit its one-dimensional phase diagram using density matrix renormalization group and, in contrast to previous work, find algebraic hastatic orders generically for stronger couplings. These are heavy Tomonaga-Luttinger liquids with nonanalyticities at Fermi vectors captured by hastatic density waves. We also find a predicted additional nonlocal order parameter due to interference between hastatic spinors, not present at large N, and residual repulsive interactions at strong coupling suggesting non-Fermi-liquid physics in higher dimensions.
The catalytic transformation of isobutene into branched liquid hydrocarbons is crucial for the production of reformulated gasoline and fuel additives. Conventional supported catalysts often lack high activity and selectivity toward the desired highly branched dimers and trimers in isobutene oligomerization. Here, by developing a tungsten single-atom catalyst (W SAC ) atomically dispersed on a silica-doped alumina (SDA) support, we report that the W SAC /SDA catalyst enables efficient and selective conversion of isobutene into highly branched C 8 and C 12 liquid olefins while suppressing the formation of heavier hydrocarbons. The atomically dispersed W 1 –O 3 moieties incorporated within the SDA support were synthesized via a high-temperature pyrolysis of a templating zinc metal–organic framework (Zn-MOF) under argon, followed by annealing in static air. The W SAC /SDA catalysts with 1.6–3.7 wt% W loading exhibited single-atom dispersion (∼0.2 nm) and outstanding performance, achieving up to 60% and 95% selectivity to branched C8 olefins at 150 °C and 250 °C, respectively, under ambient pressure. With the demonstrated high activity, selectivity, and stability, the W SAC /SDA catalyst system presents a promising platform for next-generation heterogeneous catalysts for the efficient and selective upgrading of isobutene into high-performance fuel additives.
Here, a long-standing mystery of fundamental importance in correlated electron physics is to understand strange non-Fermi liquid metals that are seen in diverse quantum materials. A striking experimental feature of these metals is a resistivity that is linear in temperature (T). In this Letter we ask what it takes to obtain such non-Fermi liquid physics down to zero temperature in a translation invariant metal. If in addition the full frequency (ω) dependent conductivity satisfies ω/T scaling, we argue that the T-linear resistivity must come from the intrinsic physics of the low energy fixed point. Combining with earlier arguments that compressible translation invariant metals are “ersatz Fermi liquids” with an infinite number of emergent conserved quantities, we obtain powerful and practical conclusions. We show that there is necessarily a diverging susceptibility for an operator that is odd under inversion and time reversal symmetries, and has zero crystal momentum. We discuss a few other experimental consequences of our arguments, as well as potential loopholes, which necessarily imply other exotic phenomena.
When a Poincaré-invariant system spontaneously breaks continuous internal symmetries, Goldstones’ theorem demands the existence of massless, spin-zero excitations in a one-to-one correspondence with the broken symmetry generators. When a system spontaneously breaks Poincaré symmetry, however, the kinds of excitations that satisfy Goldstone’s theorem can be quite unusual. In particular, they may have any spin and need not be particles or even quasiparticles. The standard coset construction used to formulate effective actions of Goldstones, however, is rather restrictive and is incapable of generating the full spectrum of possibilities allowed by Goldstone’s theorem. We propose a (partial) remedy to this problem by postulating a novel coset construction for systems that spontaneously break Poincaré symmetry. This new construction is capable of generating effective actions with a wide range of Goldstone excitations — including fermionic degrees of freedom — even when all symmetries are bosonic. To demonstrate its utility, we focus on constructing effective actions for point particles of various spins. We recover the known result that a particle of spin s requires an \( \mathcal{N} \) = 2 s supersymmetric worldline reparameterization gauge symmetry, which we implement at the level of the coset construction. In the process, we discover that massless particles require a novel kind of inverse Higgs constraint that bears some resemblance to the dynamical inverse Higgs constraints that appear in certain fermi liquid effective field theories. We then consider particles that, in addition to quantum spin, have finite spatial extent and are free to rotate. We derive a novel action for such particles and find a ‘spin-orbital’ coupling between the intrinsic quantum spin and the physical-rotation degrees of freedom.
Inherent structural and functional properties of biotechnology-derived therapeutic biologics make them susceptible to light- and temperature-induced degradation and consequently can influence their quality. Photosensitivity of therapeutic proteins continues to be examined, but the commonalities and trends of storage conditions and information about light and temperature sensitivity among currently licensed therapeutic proteins has not been previously surveyed. Using a comprehensive and relational database approach, we conducted a scientific survey of all licensed biotechnology-derived drug products with the goal of providing evidence-based information about recommended storage conditions of formulations sorted by light- and temperature-related attributes as described for each product at licensure. We report the prevalence of indications for light and temperature sensitivity in formulations categorized by their presentation type, number of doses, container type, dosage form and active molecule type. We also report the storage temperature range across formulations and diluents for reconstitution and dilution. Formulations with excipients that potentially facilitate light-induced and thermal degradation were also noted. The result of our analysis indicates that light and temperature sensitivity are prevalent across therapeutic protein formulations. However, when a formulation is reconstituted or diluted, both light and temperature sensitivity are less clear. In addition, light and temperature sensitivity are more well defined in liquid formulations than lyophilized powder formulations, and more well defined in products manufactured in autoinjectors, prefilled-syringes, and pens than products in vials. Overall, our report provides a data-driven summary of storage conditions among therapeutic protein formulations to support the development of future biologic drug products.
Direct Ink Writing (DIW) is an extrusion-based additive manufacturing method where the print medium is a liquid-phase ‘ink’ dispensed out of nozzles and deposited along digitally defined paths. Conventional DIW of thermosetting resins relies on viscosity modifying agents, novel crosslinking chemistries, and/or long curing schedules in an oven. Here we demonstrate the use of a co-planar radio frequency applicator to generate an electric field, which can be used to rapidly heat and cure nano-filled composite resins as they are printed. This method avoids the need for an oven or post- curing step. This process consists of a sequential print-and-cure cycle which allows for printing of high-resolution, multi-layered structures. Every extruded layer is partially cured using RF before depositing the next layer; this allows the printed part to maintain structural integrity. The process enables both increased throughput and decreased touch time relative to traditional manufacturing. Commercial epoxy resin with varied nano-filler loadings were examined as DIW candidates. After printing, the thermo-mechanical properties, surface finish, and shape retention of RF-cured samples were comparable to conventionally cured samples. Furthermore, this method of manufacturing establishes RF heating as a suitable alternative to conventional methods, facilitating rapid, free-form processing of thermosetting resins without a mold.
α-RuCl 3 is considered to be the top candidate material for the experimental realization of the celebrated Kitaev model, where ground states are quantum spin liquids with interesting fractionalized excitations. It is, however, known that additional interactions beyond the Kitaev model trigger in α-RuCl 3 a long-range zigzag antiferromagnetic ground state. In this work, we investigate a nanoflake of α-RuCl 3 through guarded high impedance measurements aimed at reaching the regime where the system turns into a zigzag antiferromagnet. We investigated a variety of temperatures (1.45–175 K) and out-of-plane magnetic fields (up to 11 T), finding a clear signature of a structural phase transition at ≈160 K as reported for thin crystals of α-RuCl 3 , as well as a thermally activated behavior at temperatures above ≈30 K, with a characteristic activation energy significantly smaller than the energy gap that we observe for α-RuCl 3 bulk crystals through our angle resolved photoemission spectroscopy (ARPES) experiments. Additionally, we found that below ≈30 K, transport is ruled by Efros–Shklovskii variable range hopping (VRH). Most importantly, our data show that below the magnetic ordering transition known for bulk α-RuCl 3 in the frame of the Kitaev–Heisenberg model (≈7 K), there is a clear deviation from VRH or thermal activation transport mechanisms. Finally, our work demonstrates the possibility of reaching, through specialized high impedance measurements, the thrilling ground states predicted for α-RuCl 3 at low temperatures in the frame of the Kitaev–Heisenberg model and informs about the transport mechanisms in this material in a wide temperature range.
High-concentration monoclonal antibody (mAb) formulations are often constrained by elevated viscosity, largely driven by protein–protein interactions, which complicates manufacturing and limits subcutaneous delivery. Early viscosity risk assessment is essential during discovery, yet traditional measurements require large sample volumes, and lack high-throughput capability. Here, we develop a high-throughput small-angle X-ray scattering (SAXS) protocol to detect mAb self-association at dilute concentrations, enabling early predictive insights into high-concentration viscosity. Synchrotron SAXS measurements were conducted for 21 mAbs formulated in a histidine buffer at pH 6.0. An initial subset of 10 mAbs analyzed across 1–150 mg/mL revealed that effective structure factor transitions in the low-q region, indicative of interparticle interactions, consistently emerged below 25 mg/mL. Subsequently, 11 additional mAbs were analyzed at 1–25 mg/mL using automated liquid handling and flow cells to enable high-throughput screening. High-viscosity mAbs exhibited detectable low-q upturns at concentrations ≤10 mg/mL, whereas low-viscosity mAbs showed downturns. A classification criterion based on effective structure factor transitions accurately classified all high- and low-viscosity mAbs at 150 mg/mL, offering a scalable, sample-efficient alternative to conventional methods. These results extend recent findings on the concentration-dependent sensitivity of SAXS to short-range attractions, demonstrating that they can emerge at lower concentrations than previously reported. This study presents the most comprehensive and diverse SAXS dataset for mAbs reported to date within a single formulation, providing a valuable resource for developing and validating coarse-grained models that can more accurately capture intermolecular interactions governing high-concentration solution behavior, thereby enabling rational antibody engineering and improved developability.
The leading corrections to Fermi liquid theory for non-equilibrium quasiparticle transport near a Cooper instability arise from the virtual emission and absorption of incipient Cooper pairs. We formulate the corrections to the Landau-Boltzmann transport equation starting from Keldysh's field theory for non-equilibrium, strongly interacting Fermions. The theory is applicable to quasiparticle transport in conventional and unconventional superconductors, dense nuclear matter and the low temperature phases of liquid $^3$He. Validation of the theory is provided by our analysis, and quantitative agreement between theory and experiment, of the excess attenuation of zero sound in liquid $^3$He near the superfluid transition. We propose an additional experimental test of the theory based on the effects of a Zeeman field on the spectrum of pairing fluctuations for the Cooper instability in spin-triplet superfluids.
The Japanese government is supporting development work implemented jointly by Veolia subsidiaries Kurion Japan, K.K., Veolia Nuclear Solutions (VNS), Inc., and Veolia Nuclear Solutions Federal Services, LLC for treating radioactive waste generated from Fukushima Daiichi Nuclear Power Station (NPS) water treatment using the GeoMelt{sup TM} In-Container Vitrification (ICV){sup TM} technology. The initial work consisted of glass formulation and engineering-scale testing which was completed in 2018, in the frame of an IRID (International Research Institute for Nuclear Decommissioning) program as part of a project subsidized by Japan's Ministry of Economy, Trade and Industry (METI). The Fukushima Daiichi NPS Mid- and Long-Term Road-map requires investigation of methods to stabilize solid wastes (and to immobilize radioisotopes in the wastes) generated as a result of emergency response and decommissioning activities. Cooling water treatment has resulted in a significant amount of solid and slurry secondary wastes (mostly adsorbents and ion-exchange materials) which will require processing at some point. GeoMelt{sup R} ICV{sup TM} is a joule-heated melter technology which uses a refractory-lined single-use container combining the melter and disposal container. There is no pouring required nor concerns with refractory corrosion which allows the process to accommodate a wide range of waste chemistries and high waste loadings. The testing described here consisted of three engineering-scale melts, each processing between 212 kg and 240 kg of waste simulants, glass formers, and non-radioactive cesium (Cs) and strontium (Sr) tracers. Continuous isokinetic stack sampling of off-gas emissions was performed for each test in order to calculate Cs and Sr retention in the glass wasteform. Single-pass retention of Cs in the final glass wasteform ranged from 91.46 to 99.30%, and single-pass retention of Sr ranged from 99.76 to 100%. Planned particulate recycle will increase these retention levels. Melt 1 processed a mixture of KUR-EH (a zeolite-based ion-exchange material), simulated Advanced Liquid Processing System (ALPS) Carbonate and Iron Slurries, and glass additives. Melt 2 processed a mixture of KUR-EH, KUR-TSG (a titanate-based adsorbent), and glass additives. Melt 3 processed a mixture of KUR-EH, simulated barium sulfate/iron ferrocyanide sludge (AREVA sludge), and glass additives. Waste loadings for these melts ranged from 70 weight percent (wt%) to 82 wt%. Vitrification produces a waste form much denser than the stored water treatment secondary waste wastes, resulting in significant volume reduction. Volume reductions for the three tests ranged from 74 to 79 vol%. Vitrification produces a chemically durable wasteform. Pacific Northwest National Laboratory (PNNL) tested three glass samples from each engineering-scale melt) by the Materials Characterization Center 1 (MCC-1) test, an international standard leach test of the chemical durability of nuclear waste glasses. PNNL also obtained one U.S. reference glass (EA Glass) and two Japan reference glasses P0798) and tested these under the same MCC-1 conditions (90 deg. C, 10 m-1, DIW, and 7, 14, 28-day) as the GeoMelt{sup R} ICV{sup TM} glasses. The GeoMelt{sup R} ICV{sup TM} glasses exhibited lower total normalized releases and 14- to 28-day normalized release rates than the three reference glasses. These results suggest that the GeoMelt{sup R} ICV{sup TM} glasses have durabilities on par with high-level waste glasses under standard test conditions. Post-melt process sampling and analysis indicated no Cs migration into the melter refractory materials and very little deposition of Cs or Sr onto the melter hood or off-gas piping internals. The results of the testing indicated good Cs retention in the glass, high volume reduction and waste loadings, and excellent chemical durability. These factors are important to minimize treatment costs and to protect workers and the environment. (authors)
In Performance Assessment (PA) of the Hanford Integrated Disposal Facility (IDF), 129 I is a significant contributor to the risk. The 2017 IDF PA accounted for 0.22% of the total 129 I inventory in Hanford tank waste as residing in the solidified liquid waste from the Effluent Treatment Facility (ETF). However, recent estimates suggest that higher percentages of the iodine processed at the Hanford Waste Treatment and Immobilization Plant (WTP) may be present in the liquid waste routed to the Liquid Effluent Retention Facility (LERF) for eventual treatment at the ETF. In addition, a recent integrated melter test performed at the Vitreous State Laboratory (VSL) at The Catholic University of America (CUA) showed the possibility that a significant fraction (>50%) of the total iodine in the melter feed could be present in the aqueous waste stream destined for the ETF. This stream represents a combination of the Effluent Management Facility (EMF) evaporator overhead condensate and the liquid waste from the WTP off-gas caustic scrubber. Higher levels of 129 I in this stream could affect the LERF and ETF Hazard Categorizations as well as the acceptability of the solidified ETF liquid secondary waste brine for disposal at the IDF. Accordingly, there is a need to investigate and develop potential methods and processes to mitigate this risk. Washington River Protection Solutions, LLC (WRPS) tasked Atkins and VSL to perform development and testing work to evaluate potential methods for removal of iodine species from the waste stream routed to the LERF. In particular, the testing investigated the use of an Atkins-SpinIonic™ Rotating Bed Reactor (RBR) system as a potential alternative to conventional column-based ion exchange or absorption processes. The present report provides results obtained from testing with an RBR system for the removal of iodine from simulants of the projected WTP waste stream that discharges to the LERF.
Purely quantum electron systems exhibit intriguing correlated electronic phases by virtue of quantum fluctuations in addition to electron–electron interactions. To realize such quantum electron systems, a key ingredient is dense electrons decoupled from other degrees of freedom. Here, we report the discovery of a pure quantum electron liquid that spreads up to ~3 Å in a vacuum on the surface of an electride crystal. Its extremely high electron density and weak hybridization with buried atomic orbitals show the quantum and pure nature of the electrons, which exhibit a polarized liquid phase, as demonstrated by our spin-dependent measurement. Furthermore, upon enhancing the electron correlation strength, the dynamics of the quantum electrons change to that of a non-Fermi liquid along with an anomalous band deformation, suggestive of a transition to a hexatic liquid crystal phase. Here, our findings develop the frontier of quantum electron systems and serve as a platform for exploring correlated electronic phases in a pure fashion.
A physical mixture of Ru/C and Nb 2 O 5 is an effective catalyst for upgrading lignin monomers under low H 2 pressure at 250 °C to a clean cut of hydrocarbon liquid fuels. The reaction solvent is water with a small amount of methanol additive. Hydrodeoxygenation (HDO) was evaluated using dihydroeugenol (DHE) as an exemplary lignin monomer model. Under optimized conditions, 100% conversion of DHE and very high selectivity to propyl cyclohexane (C9 hydrocarbon) was achieved. Nb 2 O 5 was prepared at a low temperature (450 °C) and was shown to contain acid sites that enhance the production of fully deoxygenated products. The methanol additive serves as a hydrogen source for the Ru/C catalysed reduction of the aromatic ring. In addition, when a substrate mixture of DHE, isoeugenol and 4-allylsyringol simulating lignin products was employed, 100% conversion to propyl cyclohexane (76%) and propyl benzene (24%) was observed, thereby suggesting the general applicability of this catalyst system for funneling lignin monomers into a clean cut of hydrocarbon liquid fuels. This study sheds light on the function of each catalyst component and provides a simple and green utilization of biomass monomers as a feedstock for renewable hydrocarbon fuels.