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At least 109 records · Page 6

Blackout Diffusion: Generative Diffusion Models in Discrete-State Spaces

Typical generative diffusion models rely on a Gaussian diffusion process for training the backward transformations, which can then be used to generate samples from Gaussian noise. However, real world data often takes place in discrete-state spaces, including many scientific applications. Here, we develop a theoretical formulation for arbitrary discrete-state Markov processes in the forward diffusion process using exact (as opposed to variational) analysis. We relate the theory to the existing continuous-state Gaussian diffusion as well as other approaches to discrete diffusion, and identify the corresponding reverse-time stochastic process and score function in the continuous-time setting, and the reverse-time mapping in the discrete-time setting. As an example of this framework, we introduce “Blackout Diffusion”, which learns to produce samples from an empty image instead of from noise. Numerical experiments on the CIFAR-10, Binarized MNIST, and CelebA datasets confirm the feasibility of our approach. Generalizing from specific (Gaussian) forward processes to discrete-state processes without a variational approximation sheds light on how to interpret diffusion models, which we discuss.

Santos, Javier E.↗

Oxygen Adsorption, Subsurface Oxygen Layer Formation and Reaction with Hydrogen on Surfaces of a Pt–Rh Alloy Nanocrystal

The oxygen adsorption and its catalytic reaction with hydrogen on Pt–Rh single crystals were studied at the nanoscale by Field Emission Microscopy (FEM) and Field Ion Microscopy (FIM) techniques at 700 K. Both FEM and FIM use samples prepared as sharp tips, apexes of which mimic a single nanoparticle of catalyst considering their similar size and morphology. Oxygen adsorption on Pt-17.4 at.%Rh samples leads to the formation of subsurface oxygen, which is manifested in the field emission (FE) patterns: for O2 exposure of ~3 Langmuir (L), {113} planes appear bright in the emission pattern, while for higher oxygen doses, i.e. 84 L, the bright regions correspond to the high index planes between the {012} and {011} planes. Formation of subsurface oxygen is probably accompanied by a surface reconstruction of the nanocrystal. The subsurface oxygen can be effectively reacted off by subsequent exposure of the sample to hydrogen gas at 700 K. The hydrogenation reaction was observed as a sudden, eruptive change of the brightness seen on the FE pattern. This reaction resulted in the recovery of the initial field emission pattern characteristic of a clean tip, with {012} facets being the most visible. It was shown that the oxygen accumulation-reduction process is completely reversible. The obtained results indicate that the presence of subsurface species must be considered in the description of reactive processes on Pt–Rh catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Millisecond Phase Transition Kinetics of Lyotropic Liquid Crystalline Nanoparticles Observed by Time‐Resolved Small Angle X‐ray Solution Scattering

This study investigates the dynamic behavior of lyotropic liquid crystal nanoparticles (LCNPs), which are widely recognized for their applications in drug delivery. By employing nanosecond near‐infrared laser pulse‐induced temperature jump (T‐jump) and time‐resolved X‐ray solution scattering, the structural dynamics of phase transitions in phytantriol‐based cubosomes and hexosomes are revealed. Both cubosome and hexosome LCNPs undergo phase transitions into noncrystalline phases at high temperatures. Their phase transition kinetics, occurring within milliseconds (ms) and involving one intermediate structure, are captured. Additionally, the reverse self‐assembly processes of LCNPs were observed, occurring on the timescale of a few hundred ms. To our knowledge, this is the first observation of LCNP T‐jump induced phase transitions on the ms timescale and their reverse self‐assembly. These findings provide valuable insights into the LCNP phase transition processes, with potential implications for drug delivery applications.

Chemistry↗

Electrolytes Polymerization‐Induced Cathode‐Electrolyte‐Interphase for High Voltage Lithium‐Ion Batteries

Abstract Lithium‐ion batteries (LIBs) based on LiNi x Co y Mn 1‐x‐y O 2 (NCM) cathode materials have been widely commercialized, because of their high energy density, favorable rate performance, and relatively low cost. However, with increased Ni content to further increase their energy density, their cycling stability deteriorates dramatically and thus fails to meet the commercial application requirements. The artificial cathode‐electrolyte‐interphase (CEI) is a promising approach to solve this problem. Here, a robust CEI is fabricated through in situ polymerization of ethylene carbonate induced by aluminum isopropoxide (AIP). By adding 1 wt.% AIP in a commercial electrolyte, the capacity retention of LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li cell at 1 C rate has been significantly increased from 80.8% to 97.8% with a highly reversible capacity of 176 mA h g −1 after 200 cycles. AIP can be also used as an additive during the slurry‐making process, enabling a reversible capacity of 170 mA h g −1 for LiCoO 2 after 200 cycles even at a high charge cut‐off voltage of 4.6 V. It is confirmed that the in situ formed CEI layer can prevent the cathodes from cracking and reduce the irreversible phase transformation.

Yang, Jixiang↗

Chemical-Biological Cyclic Process for Hexavalent Chromium Reduction to Trivalent Chromium in Aqueous Medium - 20224

Conventional treatment of chromium contamination focuses on immobilization of the highly toxic and water-soluble form Cr(VI), by reducing it to the relatively less toxic and less mobile trivalent form, Cr(III), using reducing compounds like ferrous sulfate or ferrous iron, Fe(II). The Cr(VI) also respond to biodegradation and subsequent reduction. During the reduction reaction, Fe(II) is oxidized to ferric, Fe(III), which, being at the highest oxidation state, has no ability to reduce Cr(VI), and therefore remediation process terminates. The good news is that metal-reducing bacteria, S. oneidensis MR-1, can regenerate Fe(II) from Fe(III) with the help of an organic electron donor in an appropriate bacterial media. Thus, in the Cr(VI) chemical remediation process, Fe(II) to Fe(III) conversion is reversed by the biological process, regenerating Fe(II) and the Cr(VI) chemical reduction process continues in a cyclic fashion. This study presents the results of regeneration of Fe(II) from fresh Fe(III) as well as from the reaction products of Cr(VI) and Fe(II). Both fresh Fe(III) and reaction product Fe(III) exhibited the same reduction behavior. Fe(II) production increased with the increase of initial concentration of Fe(III), resulting in 87.5% Fe(II) regeneration. The extent of Fe(III) reduction (Fe(II)t/Fe(III)0.hour) was 21 times higher than the extent of Cr(VI) reduction (Cr(VI)t/Cr(VI)0.hour) by S. oneidensis MR-1. In a cyclic process of sequential Cr(VI) addition, the amount of Fe(II) regeneration decreased with the increase in cycle number, a fixed quantity of starting S. oneidensis MR-1 could regenerate Fe(II) at least five times in a ten-hour period. More importantly, regenerated Fe(II) instantly reduced Cr(VI) to Cr(III). So, Fe(II) regeneration with metal-reducing bacteria has a good potential for application in groundwater and wastewater remediation in reducing Cr(VI) to Cr(III). As a comparison of chemical to biological transformation, chemical transformation of Cr(VI) by Fe(II) was almost 600 times greater than that of biological transformation. Therefore a chemical-biological cyclic process offers potential applications for remediation of groundwater and hexavalent chromium contaminated waste sites. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transient Studies of CO 2 Adsorption over CeO 2 Nanostructures with In Situ DRIFTS and Modulation Excitation

Experiments of in-situ DRIFTS combined with modulation excitation (ME) spectroscopy showed a rich surface chemistry associated with the adsorption of CO 2 on nanocubes and nanospheres of ceria. The nanocubes exposed faces with a (100) orientation, with the edges and corners displaying (110) and (111) orientations, respectively. Here, the nanospheres mainly contained ceria (111) and (110) planes. DFT calculations showed that CO 2 is a multidentate adsorbate on ceria that can undergo changes in its bonding configuration depending on the chemical environment. At 250 °C, a temperature typically used for the conversion of CO 2 into oxygenates, alkanes and olefins, CO 2 reacted with O centers or OH groups present on the nanocubes and nanospheres to yield bi- and tri-dentate carbonates, hydroxycarbonates, and formates. Both nanostructures were highly reactive and a dynamic equilibrium was established: carbonate species were rapidly generated upon the injection of CO 2 and they decomposed upon the removal of CO 2 from the gas phase. In the case of the ceria nanocubes, the adsorption/desorption processes were essentially reversible, opening the door to catalytic transformations. A larger concentration of defects in the ceria nanospheres led to strongly bound carbonates and formates that may be spectators, site blockers, or surface modifiers in catalytic processes. In the ME studies, additional intermediates were detected, and it was clear that the response of surface species to the presence/absence of CO 2 was highly dependent on the morphology of the ceria nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Textured Electrodes: Manipulating Built-In Crystallographic Heterogeneity of Metal Electrodes via Severe Plastic Deformation

Control of crystallography of metal electrodeposit films has recently emerged as a key to achieving long operating lifetimes in next-generation batteries. It is reported that the large crystallographic heterogeneity, e.g., broad orientational distribution, that appears characteristic of commercial metal foils, results in rough morphology upon plating/stripping. On this basis, an accumulative roll bonding (ARB) methodology—a severe plastic deformation process—is developed. Zn metal is used as a first example to interrogate the concept. It is demonstrated that the ARB process is highly effective in achieving uniform crystallographic control on macroscopic materials. After the ARB process, the Zn grains exhibit a strong (002) texture (i.e., [002] Zn //ND). The texture transitions from a classical bipolar pattern to a nonclassical unipolar pattern under large nominal strain eliminate the orientational heterogeneity of the foil. The strongly (002)-textured Zn remarkably improves the plating/stripping performance by nearly two orders of magnitude under practical conditions. The performance improvements are readily scaled to achieve pouch-type full batteries that deliver exceptional reversibility. The ARB process can, in principle, be applied to any metal chemistry to achieve similar crystallographic uniformity, provided the appropriate temperature and accumulated strains are employed. Here this concept is evaluated using commercial Li and Na foils, which, unlike Zn (HCP), are BCC crystals. The simple process for creating strong textures in both hexagonal and cubic metals and illustrating the critical role such built-in crystallography plays underscores opportunities for developing highly reversible thin metal anodes (e.g., hexagonal Zn, Mg, and cubic Li, Na, Ca, Al).

36 MATERIALS SCIENCE↗

Demo 5: RapidClave Technology Demonstrations – Round II (Task 2)

The purpose of this project task was to make automotive composite part manufacturing more cost competitive for low volume production and thereby drive composite application innovation. The strategy was to incorporate low-cost preforming, snap cure resins, and RapidClave® processing to create an alternative to conventional automotive composite manufacturing based on SMC. The program used RapidClave® technology from Globe Machine Manufacturing, fast-curing (“snap cure”) epoxy resins from Hexion, and conformable/stretchable glass fiber reinforcement mats produced by Owens Corning for rapid preforming. O’Gara Armoring retrofits vehicles to meet special security needs, such as larger doors to facilitate easier entry into the vehicle. O’Gara has a variety of custom vehicles in need of custom doors that require affordable tooling to produce approximately 100 ship sets/year. The project focused on a composite door panel application provided by O’Gara that is currently made by manual chopped fiber spray-up processing. UDRI reverse-engineered the current composite door panel and created tooling for use in the RapidClave®. UDRI designed an improved composite door using MultiMat fiberglass reinforcement from Owens Corning. UDRI made snap cure resin films from Hexion resin. Finally, UDRI conducted molding trials to compare autoclave processing with RapidClave® processing. The technical goals of the project were to reduce tooling cost by 50% as compared to SMC compression molding and to reduce cycle time by 50% compared to current manual spray-up process. The approach to reduce tool costs is based on use of single sided tooling for use at 100 psi, as compared to matched metal SMC tooling. An added benefit realized from the program is that the Owens Corning mat provided more uniform thickness and improved performance. Tensile and flexural strengths and moduli were increased by at least 50%. This task also demonstrated a 75% decrease in cycle time. O’Gara is evaluating the technology demonstrated in this project for some of their current production. Additionally, there are new products O’Gara is pursuing which require higher production rates than their current products. O’Gara has identified these new products as good candidates for the RapidClave® technology. The cost advantages demonstrated by this project would then lead to significant economic development. In conclusion, this task successfully combined the RapidClave® technology from Globe with a snap cure epoxy resin film system from Hexion and preform material from Owens Corning. Further research is needed to better map the technical limits such as cycle time of these technologies. Additionally, the technology should be extended in terms of size and shape to include large parts outside of automotive applications, such as a small aircraft fuselage.

36 MATERIALS SCIENCE↗

Dynamics of Thermally Driven Domain Transformation in Ferroelectric Thin Films

An important feature in ultrathin ferroelectric films is the spontaneous formation of nanoscale polarization domain patterns. Epitaxial strain can greatly increase the ferroelectric transition temperature such that films can be in the ferroelectric state during growth. On the other hand, depolarization fields compete with ferroelectricity in ultrathin films, and, consequently, the optimal domain configuration during growth is a moving target. Under these conditions it is readily possible for a grown film to be in a nonequilibrium domain configuration. As the energy landscape in the system is quite complex, the relaxation dynamics by which a system can evolve towards the true equilibrium configuration are also quite interesting. Here, to capture the details of this process we used Bragg-geometry x-ray photon correlation spectroscopy (XPCS), in which x-ray scattering speckle patterns contain the information from the domain arrangements inside the film. With modest heating (∼15⁢0 °C) domain relaxation from 𝑇 (tetragonal) to 𝑀 𝐶 (monoclinic) was observed in BaTiO 3 films grown on ultrathin ferroelectric PbTiO 3 layers. Two-time correlation analysis reveals fascinating details associated with sticking points and reversals in the process.

36 MATERIALS SCIENCE↗

A phase-field fracture formulation for generalized standard materials: The interplay between thermomechanics and damage

Accurately modeling fracture of ductile materials poses open challenges in the field of computational mechanics due to the multiphysics nature of their failure processes. Integrating the interplay between thermodynamics and damage into ductile fracture models is vital for predicting critical failure modes. Here, in this paper, we develop a versatile phase-field (PF) framework for modeling ductile fracture, taking into account finite-strain elasto-plasticity. The framework stems from a variational formulation of constitutive relations for generalized standard materials (GSMs), whose response is described by a Helmholtz free energy and a dissipation pseudo-potential. Its variational structure is based on a minimum principle for a functional that expresses the sum of power densities for reversible and irreversible processes. By minimizing this functional with a constraint on a von Mises yield function, we derive the evolution equation for the equivalent plastic strain and an associative flow rule. This constrained optimization problem is analytically solved for a wide class of thermo-viscoplasticity models. The key innovations of the current work include (i) a cubic plastic degradation function that accounts for a non-vanishing damage-dependent yield stress, (ii) closed-form expressions of the Helmholtz free energy and dissipation pseudo-potential for three thermo-viscoplasticity models, (iii) an extended Johnson–Cook plasticity model with a nonlinear hardening law, and (iv) a plastic work heat source that depends on the plastic degradation function and a variable Taylor–Quinney (TQ) coefficient. The capabilities of the proposed framework are tested with the aid of four ductile fracture problems, including the Sandia Fracture Challenge. In each of these problems, we examine the evolution of relevant field variables such as the PF order parameter, the equivalent plastic strain, the temperature, and the internal power dissipation density, in addition to the overall structural response quantified by the force–displacement curve. These numerical studies demonstrate that the proposed framework effectively represents ductile fracture, yielding computational results that exhibit good agreement with experimental data.

36 MATERIALS SCIENCE↗

Sign reversal in magnetic field amplification by relativistic laser-driven microtube implosions

In this work, we demonstrate and explain the surprising phenomenon of sign reversal in magnetic field amplification by the laser-driven implosion of a structured target. Relativistically intense laser pulses incident on the outer surface of a microtube target consisting of a thin opaque shell surrounding a μm-scale cylindrical void drive an initial ion implosion and later explosion capable of generating and subsequently amplifying strong magnetic fields. While the magnetic field generation is enhanced and spatially smoothed by the application of a kilotesla-level seed field, the sign of the generated field does not always follow the sign of the seed field. One unexpected consequence of the amplification process is a reversal in the sign of the amplified magnetic field when, for example, the target outer cross section is changed from square to circular. Using 2D particle-in-cell simulations, we demonstrate that sign reversal is linked to the stability of the surface magnetic field of opposite sign from the seed, which arises at the target inner surface during laser irradiation. The stability of the surface magnetic field and, consequently, the sign of the final amplified field depend sensitively on the target, laser, and seed magnetic field conditions, which could be leveraged to make laser-driven microtube implosions an attractive platform for the study of magnetic fields in high energy density plasma in regimes where sign reversal either is or is not desired.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Very high cycle fatigue characteristics of laser beam powder bed fused AlSi10Mg: A systematic evaluation of part geometry

This study explores the influence of geometry and part size on defect distribution, melt pool size, and mechanical characteristics in laser beam powder bed fused (LB-PBF) AlSi10Mg. Five distinct geometries—hourglass, small rod, small block, large block, and large rod—were fabricated under identical process parameters. Fully reversed ultrasonic fatigue testing, operating at a frequency of 20 kHz, was conducted to assess the very high cycle fatigue properties. The findings indicated that part geometry had a major impact on the fatigue properties of the material in the very high cycle fatigue regime. Specimens machined from large rods and large blocks had the lowest porosity and highest fatigue resistance. Microstructural analysis indicated that hourglass, small rod, and small block specimens had shallower melt pools and overlap depths compared to other geometries. This observation suggests a higher cooling rate in specimens with smaller cross-sectional areas, leading to the increased presence of entrapped gas pores and a lack of fusion defects. Understanding the relationship between part geometry and fatigue properties in LB-PBF components offers insights for optimizing design and manufacturing processes in additive manufacturing applications.

AlSi10Mg↗

A conformational equilibrium in the nitrogenase MoFe protein with an α-V70I amino acid substitution illuminates the mechanism of H 2 formation

Study of α-V70I-substituted nitrogenase MoFe protein identified Fe6 of FeMo-cofactor (Fe 7 S 9 MoC-homocitrate) as a critical N 2 binding/reduction site. Freeze-trapping this enzyme during Ar turnover captured the key catalytic intermediate in high occupancy, denoted E 4 (4H), which has accumulated 4[e — /H + ] as two bridging hydrides, Fe2–H–Fe6 and Fe3–H–Fe7, and protons bound to two sulfurs. E 4 (4H) is poised to bind/reduce N 2 as driven by mechanistically-coupled H 2 reductive-elimination of the hydrides. This process must compete with ongoing hydride protonation (HP), which releases H 2 as the enzyme relaxes to state E 2 (2H), containing 2[e — /H + ] as a hydride and sulfur-bound proton; accumulation of E 4 (4H) in α-V70I is enhanced by HP suppression. EPR and 95 Mo ENDOR spectroscopies now show that resting-state α-V70I enzyme exists in two conformational states, both in solution and as crystallized, one with wild type (WT)-like FeMo-co and one with perturbed FeMo-co. These reflect two conformations of the Ile residue, as visualized in a reanalysis of the X-ray diffraction data of α-V70I and confirmed by computations. EPR measurements show delivery of 2[e — /H + ] to the E 0 state of the WT MoFe protein and to both α-V70I conformations generating E 2 (2H) that contains the Fe3–H–Fe7 bridging hydride; accumulation of another 2[e — /H + ] generates E 4 (4H) with Fe2–H–Fe6 as the second hydride. E 4 (4H) in WT enzyme and a minority α-V70I E 4 (4H) conformation as visualized by QM/MM computations relax to resting-state through two HP steps that reverse the formation process: HP of Fe2–H–Fe6 followed by slower HP of Fe3–H–Fe7, which leads to transient accumulation of E 2 (2H) containing Fe3–H–Fe7. In the dominant α-V70I E 4 (4H) conformation, HP of Fe2–H–Fe6 is passively suppressed by the positioning of the Ile sidechain; slow HP of Fe3–H–Fe7 occurs first and the resulting E 2 (2H) contains Fe2–H–Fe6. Importantly, it is this HP suppression in E 4 (4H) that enables α-V70I MoFe to accumulate E 4 (4H) in high occupancy. In addition, HP suppression in α-V70I E 4 (4H) kinetically unmasks hydride reductive-elimination without N 2 -binding, a process that is precluded in WT enzyme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox‐Active Frustrated Lewis Pair‐Mediated B—H Bond Activation: From Proton Transfer to THF Ring Opening

The CAAC-stabilized dithiolene (L 0 ) zwitterion (1), an unusual redox-active intramolecular frustrated Lewis pair (FLP), activates the B─H bond of boranes via hydride-coupled reverse electron transfer processes. The reactions of 1 with catecholborane in THF give a zwitterionic bis(dithiolene)-based spiroborate ( 2 ), in which one sulphur atom (at the C2 carbon) bonds to the (CH 2 ) 4 OB(O) 2 C 6 H 4 chain due to the catecholborane (CatBH)/S thiourea Lewis pair-mediated THF ring opening. In addition to 2 , [CAAC(H)] + [(Cat) 2 B] − , ( 3 ), CAAC(H) 2 , ( 4 ), and [CAAC(H) 3 ] + [(Cat) 2 B] − , ( 5 ), are also isolated from these reactions. In addition to synthetic, structural, and spectroscopic data, a plausible reaction mechanism is proposed. This finding provides compelling experimental evidence of FLP-mediated B─H activation via net proton transfer.

carbenes↗

Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe 3 ) 2 , O t Bu) with an Iridium Hydride

Abstract Reactions of the Ir V hydride [ Me BDI Dipp ]IrH 4 {BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐ i Pr 2 C 6 H 3 } with E[N(SiMe 3 ) 2 ] 2 (E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐E) 2 in good yields. Moreover, ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐Ge) 2 was formed in situ from thermal decomposition of [ Me BDI Dipp ]Ir(H) 2 Ge[N(SiMe 3 ) 2 ] 2 . These reactions are accompanied by liberation of HN(SiMe 3 ) 2 and H 2 through the apparent cleavage of an E−N(SiMe 3 ) 2 bond by Ir−H. In a reversal of this process, ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐E) 2 reacted with excess H 2 to regenerate [ Me BDI Dipp ]IrH 4 . Varying the concentrations of reactants led to formation of the trimeric ([ Me BDI Dipp ]IrH 2 ) 3 ( μ 2 ‐E) 3 . The further scope of this synthetic route was investigated with group 15 amides, and ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐Bi) 2 was prepared by the reaction of [ Me BDI Dipp ]IrH 4 with Bi(NMe 2 ) 3 or Bi(O t Bu) 3 to afford the first example of a “naked” two‐coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir 2 E 2 (E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir 2 Bi 2 is characterized as having a closed‐shell singlet ground state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗