Separation of bio-based glucaric acid via antisolvent crystallization and azeotropic drying
A downstream process was developed for producing pure monopotassium glucarate and crystalline glucaric acid from a fermentation broth.
Choi, Hoon↗
SEARCH · Engineering Papers
Results for “CRYSTALS”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Modeling dark- and light-induced crystal structures and single-crystal optical absorption spectra of ruthenium-based complexes that undergo SO 2 -linkage photoisomerization
A family of coordination complexes of the type [Ru(SO 2 )(NH 3 ) 4 X] m+ Y n – (m, n = 1 or 2) exhibit optical switching capabilities in their single-crystal states. This striking effect is caused by the light-induced formation of SO 2 -linkage photoisomers, which are metastable if kept at suitably cool temperatures. We modeled the dark- and light-induced states of these large crystalline complexes via plane-wave (PW)- and molecular-orbital (MO)-based density functional theory (DFT) and time-dependent DFT in order to calculate their structural and optical properties; the calculated results are compared with experimental data. We show that the PW-DFT-based periodic models replicate the structural properties of these complexes more effectively than the MO-DFT-based molecular-fragment models, observing only small deviations in key bond lengths relative to the experimentally derived crystal structures. The periodic models were also found to more effectively simulate trends seen in experimental optical absorption spectra, with optical absorbance and coverage of the visible region increasing with the formation of the photoinduced geometries. The contribution of the metastable photoisomeric species more heavily focuses on the lower-energy end of the spectra. Spectra generated from the molecular-fragment models are limited by the geometry of the fragment used and the number of excited-state roots considered in those calculations. In general, periodic models outperform the molecular-fragment models owing to their ability to better appreciate the periodic phenomena that are present in these crystalline materials as opposed to MO approaches, which are finite methods. We thus demonstrate that PW-DFT-based periodic models should be considered as a more than viable method for simulating the optical and electronic properties of these single-crystal optical switches.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Liquid Crystal Orientation and Shape Optimization for the Active Response of Liquid Crystal Elastomers
Liquid crystal elastomers (LCEs) are responsive materials that can undergo large reversible deformations upon exposure to external stimuli, such as electrical and thermal fields. Controlling the alignment of their liquid crystals mesogens to achieve desired shape changes unlocks a new design paradigm that is unavailable when using traditional materials. While experimental measurements can provide valuable insights into their behavior, computational analysis is essential to exploit their full potential. Accurate simulation is not, however, the end goal; rather, it is the means to achieve their optimal design. Such design optimization problems are best solved with algorithms that require gradients, i.e., sensitivities, of the cost and constraint functions with respect to the design parameters, to efficiently traverse the design space. In this work, a nonlinear LCE model and adjoint sensitivity analysis are implemented in a scalable and flexible finite element-based open source framework and integrated into a gradient-based design optimization tool. To display the versatility of the computational framework, LCE design problems that optimize both the material, i.e., liquid crystal orientation, and structural shape to reach a target actuated shapes or maximize energy absorption are solved. Multiple parameterizations, customized to address fabrication limitations, are investigated in both 2D and 3D. The case studies are followed by a discussion on the simulation and design optimization hurdles, as well as potential avenues for improving the robustness of similar computational frameworks for applications of interest.
42 ENGINEERING↗
The crystal structure of Fe2S at 90 GPa based on single-crystal X-ray diffraction techniques
The Fe-S system was explored in a laser-heated diamond-anvil cell at 89(2) GPa and 2380(120) K to better understand the phase stability of Fe 2 S. Upon temperature quenching, crystallites of Fe 2 S were identified, and their structure was investigated using single-crystal X-ray diffraction techniques. At these conditions, Fe 2 S adopts the C23 structure (anti-PbCl 2 , Co 2 P) with space group Pnma (Z = 4). This structure consists of columns of corner-sharing, FeS 4 tetrahedra, and columns of edge-sharing FeS 5 square pyramids linked along edges in the b direction. Sulfur is in ninefold coordination with Fe. This work marks the first high-pressure structural solution and refinement of Fe 2 S synthesized in a multigrain Fe+FeS sample at 90 GPa and 2400 K and establishes the stability of C23 Fe 2 S at these conditions. A previous powder diffraction study reports an orthorhombic Fe 2 S phase with a C37, Co 2 Si-like unit cell above 190 GPa. A C23–C37 structural transition is inferred to explain the previously observed unit-cell parameters at higher pressures and temperatures. These results highlight the utility of applying single-crystal X-ray diffraction techniques to high P-T multigrain samples to explore the structural properties of iron-rich phases in Earth and planetary cores.
36 MATERIALS SCIENCE↗
An Atomic View of Cation Diffusion Pathways from Single;#8208;Crystal Topochemical Transformations
Abstract not provided
Handy, Joseph V.↗
Synthesis, Crystal and Electronic Structure of Layered AM Sb Compounds ( A = Rb, Cs; M = Zn, Cd): Synthesis, Crystal and Electronic Structure of Layered AM Sb Compounds ( A = Rb, Cs; M = Zn, Cd)
Synthesis, crystal structure, thermal stability, and electronic band structure of four new metal antimonides AMSb (A = Rb, Cs; M = Zn, Cd) are reported. CsZnSb and RbZnSb crystallize in the hexagonal ZrBeSi structure type, in a P6 3 /mmc space group (no. 194, Z = 2) and unit cell dimensions of a = 4.5588(2)/4.5466(4) Å and c = 11.9246(6)/11.0999(10) Å. CsCdSb and RbCdSb crystallize in the tetragonal PbFCl structure type in a P4/nmm space group (no. 129; Z = 2) and unit cell parameters of a = 4.8884(5)/4.8227(3) Å and c = 8.8897(9)/8.5492(7) Å. All four compounds are air- and water-sensitive and are shown through DSC measurements to decompose between 975 K and 1060 K. Analysis of the calculated electronic band structure shows that the Zn-containing antimonides are topologically trivial narrow bandgap semiconductors, whereas Cd-containing compounds exhibit a band inversion along Γ-Z direction.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Two Polymorphs of BaZn 2 P 2 : Crystal Structures, Phase Transition, and Transport Properties
Here, the novel α-BaZn 2 P 2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elu-cidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu 2 S 2 structure type, with unit cell parameters a = 9.7567(14) Å, b = 4.1266(6) Å, and c = 10.6000(15) Å. With β-BaZn 2 P 2 being previously iden-tified as belonging to the ThCr 2 Si 2 family, and with the precedent of structural phase transitions between the α-BaCu 2 S 2 type and the ThCr 2 Si 2 type, the potential for the pattern to be extended to the two different structural forms of BaZn 2 P 2 was explored. Thermal analysis suggest that a first order phase transition occurs at ~1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal β-BaZn 2 P 2 ; the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn 2 P 2 is a p-type, narrow-gap semiconductor with a direct bandgap (Eg) of 0.5 eV. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 µV/K to 184 µV/K at 600 K. The electrical resistivity of α-BaZn 2 P 2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradual decrease upon heating. Such behavior is comparable to those of the typical semimetals or degenerate semiconductors. Although the observed values of the as-synthesized samples are not optimal, the carrier concentration can apparently be tuned to fall between the values of metals and semiconductors, thus providing an open window for optimizing this phase towards achieving an enhanced thermoelectric figure of merit zT. The calculated indirect band gap for the β-BaZn 2 P 2 phase is Eg = 0.03 eV which is about an order of magnitude lower than that of α-BaZn 2 P 2 . It is expected that the cage-like structural motif and layered structure possessed by α-BaZn 2 P 2 and β-BaZn 2 P 2 phases, respectively, would promote the realiza-tion of a low thermal conductivity in both compounds.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Nanoscale Periodic Trapping Sites for Interlayer Excitons Built by Deformable Molecular Crystal on 2D Crystal
The nanoscale moiré pattern formed at 2D transition-metal dichalcogenide crystal (TMDC) heterostructures provides periodic trapping sites for excitons, which is essential for realizing various exotic phases such as artificial exciton lattices, Bose–Einstein condensates, and exciton insulators. At organic molecule/TMDC heterostructures, similar periodic potentials can be formed via other degrees of freedom. Here, we utilize the structure deformability of a 2D molecular crystal as a degree of freedom to create a periodic nanoscale potential that can trap interlayer excitons (IXs). Specifically, two semiconducting molecules, PTCDI and PTCDA, which possess similar band gaps and ionization potentials but form different lattice structures on MoS 2 , are investigated. The PTCDI lattice on MoS 2 is distorted geometrically, which lifts the degeneracy of the two molecules within the crystal’s unit cell. The degeneracy lifting results in a spatial variation of the molecular orbital energy, with an amplitude and periodicity of ~0.2 eV and ~2 nm, respectively. On the other hand, no such energy variation is observed in PTCDA/MoS 2 , where the PTCDA lattice is much less distorted. Furthermore, the periodic variation in molecular orbital energies provides effective trapping sites for IXs. For IXs formed at PTCDI/MoS 2 , rapid spatial localization of the electron in the organic layer toward the interface is observed, which demonstrates the effectiveness of these interfacial IX traps.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Selective signalling of alcohols by a molecular lattice and mechanism of single-crystal-to-single-crystal transformations
A molecular material undergoes spin-switching as it exchanges MeOH, EtOH or n PrOH with acetone from the lattice. The subsequent thermal single-crystal-to-single-crystal desorption of n PrOH is followed by single crystal X-ray diffraction snapshots.
Costa, José Sánchez↗
The association of structural chirality and liquid crystal anchoring in polymer stabilized cholesteric liquid crystals
Polymer stabilized cholesteric liquid crystals (PSCLCs) are electrically reconfigurable reflective elements. Prior studies have hypothesized and indirectly confirmed that the electro-optic response of these composites is associated with the electrically mediated distortion of the stabilizing polymer network. The proposed mechanism is based on the retention of structural chirality in the polymer stabilizing network, which upon deformation is spatially distorted, which accordingly affects the pitch of the surrounding low molar-mass liquid crystal host. Here, we utilize fluorescent confocal polarized microscopy to directly assess the electro-optic response of PSCLCs. By utilizing dual fluorescent probes, sequential imaging experiments confirm that the periodicity of the polymer stabilizing network matches that of the low molar-mass liquid crystal host. Further, we isolate distinct ion-polymer interactions that manifest in certain photopolymerization conditions.
Radka, Brian P.↗
Surface co-crystallization with an organic single crystal enables vapochromic and luminescent detection of phenols
Single crystals of an organic semiconductor undergo surface co-crystallization with phenol vapors, producing color and luminescence changes. The process is reversible, enabling solid-state sensing through hydrogen bonding at the crystal surface.
Bondarenko, Ivan [Department of Chemistry, Reed Co↗
Probing the lattice structure of dynamically compressed and released single crystal iron through the alpha to epsilon phase transition
In this work, experiments using broadband Laue x-ray diffraction (XRD) were used to examine the lattice structure of dynamically compressed [100]-oriented single crystal iron samples at the Dynamic Compression Sector at the Advanced Photon Source. These experiments used 1 μm thick iron single crystal samples sandwiched between a polyimide ablator and a polycarbonate window. A 100 J, 10 ns duration laser pulse incident on the polyimide ablator was used to shock compress the iron samples to initial stresses greater than 25 GPa, exceeding the ~13 GPa alpha (body-centered-cubic or bcc structure) to epsilon (hexagonal-close-packed or hcp structure) phase transition stress. XRD measurements were performed at various times relative to the shock wave entering the iron sample: early times, <~150 ps while the initial shock waves propagated through the iron; intermediate times, after the iron equilibrated with the ablator and window reaching a plateau stress state (12 or 17 GPa) lasting several nanoseconds; and late times, during uniaxial strain release. The early time measurements show that in <~150 ps, the high-pressure hcp phase is relaxed with a c/a ratio of 1.61, contrary to previous laser shock experiments where a c/a ratio of 1.7 was inferred. In the plateau stress state and partially released states, XRD measurements showed that the hcp structure retained a c/a ratio of 1.61 with no observable changes in the microstructure. Upon stress release at ~1 GPa/ns release rate, the reverse phase transition (hcp to bcc) to the original single crystal orientation (implying a transformation memory effect) was observed to reach completion somewhere between 13 and 11 GPa, indicating little stress hysteresis under rapid uniaxial strain release. A similar memory effect for the reverse hcp to bcc transformation has been previously observed under hydrostatic compression. However, the bcc/hcp orientation relationships differ somewhat between dynamic and static compression experiments, implying that the transformation pathway under uniaxial dynamic strain differs from the Burgers mechanism.
36 MATERIALS SCIENCE↗
Telecommunication-wavelength two-dimensional photonic crystal cavities in a thin single-crystal diamond membrane
We demonstrate two-dimensional photonic crystal cavities operating at telecommunication wavelengths in a single-crystal diamond membrane. We use a high-optical-quality and thin (~300 nm) diamond membrane, supported by a polycrystalline diamond frame, to realize fully suspended two-dimensional photonic crystal cavities with a high theoretical quality factor of ~8 × 10 6 and a relatively small mode volume of ~2(λ/n) 3 . The cavities are fabricated in the membrane using electron-beam lithography and vertical dry etching. We observe cavity resonances over a wide wavelength range spanning the telecommunication O- and S-bands (1360–1470 nm) with Q factors of up to ~1800. Our method paves the way for on-chip diamond nanophotonic applications in the telecommunication-wavelength range.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Crystal response measurement of the x-ray transmission crystals used by the Imaging Spectroscopy Snout at the National Ignition Facility
The Imaging Spectroscopy Snout (ISS) used at the National Ignition Facility is able to simultaneously collect neutron pinhole images, 1D spatially resolved x-ray spectra, and time resolved x-ray pinhole images. To measure the x-ray spectra, the ISS can be equipped with up to four different transmission crystals, each offering different energy ranges from ∼7.5 to ∼12 keV and different resolutions. Characterizing and calibrating such instruments is of paramount importance in order to extract meaningful results from experiments. More specifically, we characterized different ISS transmission-type alpha-Quartz crystals by measuring their responses as a function of photon energy, from which we inferred the angle-integrated reflectivity for each crystal’s working reflections. These measurements were made at the Lawrence Livermore National Laboratory calibration station dedicated to the characterization of x-ray spectrometers. The sources used covered a wide x-ray range—from a few to 30 keV; the source diameter was ∼0.6 mm. The experimental results are discussed alongside theoretical calculations using the pyTTE model.
Dozieres, M. (ORCID:0000000286401459)↗
Crystal Growth of Cesium Hafnium Chloride (Cs2HfCl6) Scintillating Crystal
Crystal growth is the process where crystalline substance forms and increases in size through the addition of atoms, ions, or molecules. In this research we used the Bridgman technique to grow Cesium Hafnium Chloride (C2HfCl6). This technique is ideal for growing large volume crystal. Using a vertical furnace with two heating zones for heating and cooling. the material solidifies into a crystal as it slowly transitions from hot to cold zone.
Tribble, Jalen↗
Crystal chemistry at high pressure
The chemistry we are taught in school, and we experience in our daily existence occurs at 1 atm. However, pressure spans an astounding 62 orders of magnitude in the Universe in going from the void of interstellar space to the crushing conditions at the center of a neutron star. The way in which pressure affects chemistry is important for Earth and planetary sciences, materials science, in understanding the extreme conditions experienced in nuclear explosions, and it may be key in addressing the future energy needs of our society. In this article we outline how the often neglected pressure variable affects chemistry, beginning from the way in which atomic energy levels are altered. This lays the foundation for understanding the unique crystal and electronic structures that emerge when matter is squeezed, as well as pressure’s effect on chemical reactivity. Finally, we give an overview of the main concepts behind conventional, or phonon-mediated, superconductivity, and describe how the pressure variable may be key in discovering and designing light-element based materials whose superconducting critical temperatures approach room temperature. Here, we discuss some of the main families of superconducting hydrides that have been predicted computationally, and the experimental successes in this exciting and rapidly developing field.
Chemical bonding↗
Single‐Crystal to Single‐Crystal Transformations: Stepwise CO 2 Insertions into Bridging Hydrides of [(NHC)CuH] 2 Complexes
Abstract Mechanistic studies of substrate insertion into dimeric [(NHC)CuH] 2 (NHC=N‐heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single‐crystal to single‐crystal (SC‐SC) transformations, we discovered a new pathway of stepwise insertion of CO 2 into [(NHC)CuH] 2 without complete dissociation of the dimer. The first CO 2 insertion into dimeric [(IPr*OMe)CuH] 2 (IPr*OMe=N,N′‐bis(2,6‐bis(diphenylmethyl)‐4‐methoxy‐phenyl)imidazole‐2‐ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐H). A second CO 2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu] 2 (μ‐1,3‐O 2 CH)(μ‐1,1‐O 2 CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗