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Kinetics and Rheological Behavior of Higher Solid (Solids >20%) Enzymatic Hydrolysis Reactions Using Dilute Acid Pretreated, Deacetylation and Disk Refined, and Deacetylation and Mechanical Refined (DMR) Corn Stover Slurries
Many potential biochemical pathways producing advanced hydrocarbon fuels from renewable lignocellulosic biomass require hydrolysates with high sugar concentrations and low toxicity, enabling flexible fermentation strategies, such as fed-batch fermentations capable of producing high product titers and production rates during fermentation. High sugar concentrations also increase the osmotic pressure in the hydrolysates, thus helping to decrease contamination issues. We have shown the production of high sugar concentrations directly from biomass without the need for energy/capital intensive concentration, conditioning, and/or purification steps. In our previous work, we successfully demonstrated high biomass-derived sugar concentrations (over 230 g/L fermentable sugars) in enzymatic hydrolysis from high solid (>20 wt % insoluble solids) digestions of dilute alkali deacetylated and mechanically refined (DMR) corn stover slurries. The goal of this work was to understand the effects of initial solid loadings on differently pretreated corn stover substrates on the rheological property changes of enzymatic-hydrolyzed slurries as well as the rates and yields of the enzymatic hydrolysis reactions. We performed high-solid enzymatic hydrolysis using deacetylated and disk refined (DDR), DMR, and dilute acid pretreated (DAP) corn stover substrates at four different initial total solid loadings, 17, 22, 27, and 32%. Slurry samples were collected at regular intervals for measurements of monomeric and oligomeric sugar concentrations (glucose and xylose), particle size distributions, viscosities, and yield stresses. We produced over 270 g/L of fermentable, monomeric sugars (157 g/L of glucose and 114 g/L of xylose) at 32 wt % total insoluble solid during enzymatic hydrolysis of the DMR substrates. The pumpabilities of the digested, high-solid enzymatic hydrolysates were shown to be comparable to other commercially relevant slurry streams, such as honey, peanut butter, and ketchup from the food industry. The conversion and rheological results indicate that high-solid enzymatic hydrolysis (~33 wt %) of DMR substrates is a promising and scalable technology for producing high sugar concentration slurries from lignocellulosic biomass.
A directional microcrack damage theory for brittle solids based on continuous hyperplasticity
We present a novel microcrack-damage theory for brittle solids under compression. Instead of using internal variables like zeroth, second or fourth rank damage tensors, the state of material damage is represented by an internal function that encapsulates the information of direction, density and size of microcracks. Just like other internal variables, the evolution of this state function must obey the second law of thermodynamics for arbitrary loading paths. This is done by casting the model in the framework of continuous hyperplasticity and enforcing a non-negative dissipation rate functional. The proposed framework offers predictions on the continuous evolution of microcrack density and the induced material anisotropy along with the macroscopic stress-strain curves. The use of continuous damage function grants the model significantly enhanced resolution in characterizing the direction-dependent response of cracked solids compared to classical models that are based on damage tensors. Two scenarios are considered in developing the theory, one assumes frictionless cracks and the other incorporates friction between crack surfaces. The results highlight that inelasticity, pressure dependence, and loading-unloading hysteresis exhibited by brittle solids are natural consequences of frictional microcracks. The proposed theory offers a generic and versatile framework to upscale micromechanical processes operating at individual crack scale to explain the macroscopic behavior of cracked solids.
Response of Solid He-4 to External Stress: Interdigital Capacitor Solid Level Detector and Optical Interferometer
Two experiments are being conducted to observe the liquid/solid interface of He-4 near 1 K. Interesting instabilities are expected to occur when the solid is non-hydrostatically stressed. (1)A compact interdigital capacitor is used as a level detector to observe solid He-4 to which stresses are applied externally. The capacitor consists of 38 interlaced 50 m wide and 3.8 mm long gold films separated by 50 m and deposited onto a 5 mm by 5 mm sapphire substrate. The capacitor is placed on one flat end wall of a cylindrical chamber (xx mm diameter and xx mm long). The solid is grown to a known height and a stress is applied by a tubular PZT along the cylindrical axis. The observed small change in height of the solid at the wall is linearly proportional to the applied stress. The solid height decreases under compressive stress but does not change under tensile stress. The response of the solid on compressive stress is consistent with the expected quadratic dependence on strain. (2)Interferometric techniques are being developed for observing the solid He-4 surface profile. A laser light source is brought into the low temperature region via single mode optical fiber. The interference pattern is transmitted back out of the low temperature apparatus via optical fiber bundle. The solid He-4 growth chamber will be equipped with two PZT's such that stress can be applied from orthogonal directions. Orthogonally applied stress is expected to induce surface instability with island-like deformation on a grid pattern. Apparatus design and progress of its construction are described.
Architectural design and fabrication approaches for solid-state batteries
Solid-state batteries are promising candidates for energy storage due to their potential advantages in safety, working temperature range, and energy density compared to traditional liquid-electrolyte-based batteries. Rational battery architecture design and a scalable fabrication approach are critical to realize solid-state batteries. In this article, we present the architecture, fabrication procedure, and related challenges of sulfide and oxide electrolyte-based solid-state batteries. Approaches toward intimate solid–solid contact, thin solid-electrolyte fabrication, and scale-up production are discussed. Lastly, we discuss the future research directions of solid-state batteries.
Realizing high-capacity all-solid-state lithium-sulfur batteries using a low-density inorganic solid-state electrolyte
Abstract Lithium-sulfur all-solid-state batteries using inorganic solid-state electrolytes are considered promising electrochemical energy storage technologies. However, developing positive electrodes with high sulfur content, adequate sulfur utilization, and high mass loading is challenging. Here, to address these concerns, we propose using a liquid-phase-synthesized Li 3 PS 4 -2LiBH 4 glass-ceramic solid electrolyte with a low density (1.491 g cm −3 ), small primary particle size (~500 nm) and bulk ionic conductivity of 6.0 mS cm −1 at 25 °C for fabricating lithium-sulfur all-solid-state batteries. When tested in a Swagelok cell configuration with a Li-In negative electrode and a 60 wt% S positive electrode applying an average stack pressure of ~55 MPa, the all-solid-state battery delivered a high discharge capacity of about 1144.6 mAh g −1 at 167.5 mA g −1 and 60 °C. We further demonstrate that the use of the low-density solid electrolyte increases the electrolyte volume ratio in the cathode, reduces inactive bulky sulfur, and improves the content uniformity of the sulfur-based positive electrode, thus providing sufficient ion conduction pathways for battery performance improvement.
Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries
All-solid-state battery is considered as one of the most promising competitors to Li ion batteries. Two widely known performance metrics for solid electrolytes, among others, are ionic conductivity and stability. In this study, it is found that both can be improved by the synergistic effects of chlorine substitution in sulfide-based solid electrolytes. Particularly, instabilities arising from both bulk decompositions and interfacial reactions to electrodes can be better inhibited in the chlorine substituted sulfide solid electrolytes through the increased susceptibility to the mechanical constriction induced enhancement of voltage stability. As a result, the stability window of some chlorine-rich Li-argyrodites can be systematically higher than some other chlorine-deficient or chlorine-free electrolytes, especially under the implementation of the mechanical constriction battery assembly and test conditions. Thus, a solid-state battery system of 4 V to 5 V-class cathodes paired with lithium metal anode is demonstrated using these chlorine-rich Li-argyrodites without additional coatings. Furthermore, since Cl composition modulates the stability and instability of Li-argyrodite at low voltages, it allows us to design a multilayer configuration with a hierarchy of Li metal stabilities to demonstrate the stable cycling at relatively high current densities for solid-state batteries. It is found that a moderate Cl composition in the electrolyte is the best to inhibit Li dendrite penetration as the central electrolyte layer, emphasizing a slightly increased “instability” as the hidden performance metric of relevance here, in addition to the two well-known metrics of stability and ionic conductivity. The understanding of the chlorine substitution effect in sulfide electrolytes provides an important design principle for all-solid-state batteries.
NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery
Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.
Multiphase phase-field approach for solid–solid phase transformations via propagating interfacial phase in HMX
In this study, a thermodynamically consistent multiphase phase-field theory has been formulated to describe temperature-induced solid–solid phase transformations via an interfacial phase. This theory satisfies all thermodynamic equilibrium and stability conditions. It allows us to formulate the analytical solutions of the interface profile, energy, width, and velocity for each of the propagating solid–melt and solid–solid interfaces. The formation of the intermediate melt during solid–solid phase transformation has been studied hundreds of degrees below melting temperature in the HMX energetic crystal. The effect of the penalizing term in the phase-field model and two nanoscale material parameters on the appearance and degree of disordering of intermediate melt has been analyzed for the non-equilibrium interface. The developed approach is applicable to phase transitions in geological, pharmaceutical, ferroelectric, colloidal, and superhard materials where phase transformations occur via the intermediate phase.
System and method and apparatus for maintaining a pressure balance in a solids flow loop and for controlling the flow of solids therethrough
A system includes a standpipe for receiving a flow of solids therethrough, the standpipe having at least one inlet configured to receive a gas for decreasing a solids-to-gas ratio of the flow, a sealpot having an inlet fluidly coupled to the standpipe and an outlet fluidly coupled to a riser, the sealpot being configured to fluidize the solids received from the standpipe and to transport the solids to the riser, and a drain device fluidly coupled to an outlet in the standpipe, the outlet being located upstream from the inlet of the sealpot. The drain device is configured to remove the excess gas from the flow of solids within the standpipe to increase the solids-to-gas ratio of the flow prior to the solids entering the sealpot.
Solid-solid phase transition via the liquid in a Pd 43 Cu 27 Ni 10 P 20 bulk metallic glass under conventional conditions
The microscopic mechanism of solid-solid phase transitions is a long-standing fundamental issue in materials science. Here we directly report the experimental evidence of the existence of an intermediate liquid during the solid-solid phase transition in a bulk Pd 43 Cu 27 Ni 10 P 20 alloy by in situ high temperature high energy X-ray diffraction, combined with the differential scanning calorimetry at slow heating rates down to 5 K/min. We elucidate that this intermediate liquid is attributed to the melting of the low-melting-point crystalline phases, rather than induced by the elastic stress energy along the interface proposed in literatures. This could also be a general feature in multicomponent alloys if a low-melting-point crystalline phase is formed together with other crystalline phases during heating. Furthermore, all results obtained here are scientifically sound and provide new insight into the phase transition theory, which will trigger more studies on the microscopic mechanism of solid-solid phase transition via an intermediate liquid.
Operation and Control of Soft Switching Solid State Transformer as a Virtual Synchronous Machine for Photovoltaic Application
Possibility for control and operation of a three-phase solid state soft switching transformer based as a virtual synchronous machine or synchronverter has been investigated in this paper. The soft switching solid state transformer is used as an interface between the ac grid and a photovoltaic power generation unit supported by a battery bank. The control architecture investigated in this paper is that of a synchronverter to achieve inertial support to the grid and local loads. The operation of the soft switching solid state transformer has also been investigated as a V S M during unbalanced/distorted grid voltage condition. Control objective to achieve oscillation free power transfer between the ports (photovoltaic, battery and grid) has been achieved. The presented architecture has been verified for several important case studies via numerical simulations based on MATLAB/Simulink domain.
Design of a gas-solid-solid separator to remove ash from circulating fluidized bed reactors
Cyclones are one of the most common types of gas-solid separators used in circulating fluidized bed boilers. However, cyclones typically do not allow ash to leave the system through the cyclone exit, causing ash to build up in the fluidized bed and necessitating additional systems to remove ash that builds up in the bed. In this study, an alternative “disengager” gas-solid separator is proposed as a way of inherently separating small and large solids, resulting in a gas-solid-solid separation system where ash is allowed to leave the system along with gas while the desired fluidized bed material is retained. Unlike cyclones, which rely on centrifugal force to separate solids and gas, the disengager separates based on entrainment velocity of the particles. Upwards-flowing gas and particles strike a deflection plate and enter the disengaging chamber where particles with low terminal velocity such as ash fines flow with the gas, while larger particles such as sand fall to the bottom of the separator and are returned to the fluidized bed. In this study, several different proposed disengager configurations are simulated and compared to a typical cyclone using computational fluid dynamic (CFD) simulations. Furthermore, it was found that separation efficiency in the disengager is strongly influenced by the size of the deflection plate, rather than by the size of the unit itself. The predicted separation efficiency showed that compared to a cyclone, the disengager design allows significantly more ash to exit the system but retains a similar amount of desirable material. Additionally, the disengager was predicted to not suffer significantly more erosion that a cyclone.
Three-dimensional atomic packing in amorphous solids with liquid-like structure
Liquids and solids are two fundamental states of matter. However, our understanding of their three-dimensional atomic structure is mostly based on physical models. Here we use atomic electron tomography to experimentally determine the three-dimensional atomic positions of monatomic amorphous solids, namely a Ta thin film and two Pd nanoparticles. We observe that pentagonal bipyramids are the most abundant atomic motifs in these amorphous materials. Instead of forming icosahedra, the majority of pentagonal bipyramids arrange into pentagonal bipyramid networks with medium-range order. Molecular dynamics simulations further reveal that pentagonal bipyramid networks are prevalent in monatomic metallic liquids, which rapidly grow in size and form more icosahedra during the quench from the liquid to the glass state. Furthermore, these results expand our understanding of the atomic structures of amorphous solids and will encourage future studies on amorphous–crystalline phase and glass transitions in non-crystalline materials with three-dimensional atomic resolution.
Perspective: Nonequilibrium dynamics of localized and delocalized excitons in colloidal quantum dot solids
Self-assembled quantum dot (QD) solids are a highly tunable class of materials with a wide range of applications in solid-state electronics and optoelectronic devices. In this perspective, the authors highlight how the presence of microscopic disorder in these materials can influence their macroscopic optoelectronic properties. Specifically, they consider the dynamics of excitons in energetically disordered QD solids using a theoretical model framework for both localized and delocalized excitonic regimes. In both cases, they emphasize the tendency of energetic disorder to promote nonequilibrium relaxation dynamics and discuss how the signatures of these nonequilibrium effects manifest in time-dependent spectral measurements. Moreover, they describe the connection between the microscopic dynamics of excitons within the material and the measurement of material specific parameters, such as emission linewidth broadening and energetic dissipation rate.
Investigation of a Solid-State Tuning Behavior in Lithium Niobate
Electric field-based frequency tuning of acoustic resonators at the material level provides an enabling technology for building complex tunable filters. Tunable acoustic resonators were fabricated in thin plates (h/λ ~ 0.05) of X-cut lithium niobate (90°, 90°, ψ = 170°). Lithium niobate is known for its large electromechanical coupling (SH: K 2 40%) and thus applicability for low-insertion loss and wideband filter applications. We demonstrate the effect of a DC bias to shift the resonant frequency by ~0.4% by directly tuning the resonator material. The mechanism is based on the nonlinearities that exist in the piezoelectric properties of lithium niobate. Devices centered at 332 MHz achieved frequency tuning of 12 kHz/V through application of a DC bias.