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Results for “MECHANICAL FORCE”

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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Multi-state Catalysts Modulated by Mechanical Force (Final Report)

The development of more efficient catalytic processes and new approaches to control catalytic activity and selectivity are central to the realization of more selective, atom economic, and energy efficient routes to value added chemicals and polymers. The reactivity and selectivity of a transition metal catalyst is intimately related to the ligand-sphere geometry and, in many cases, the ideal ligand geometry for one step of a catalytic cycle is poorly matched to the ideal ligand geometry for another, resulting in sub-optimal efficiency. Macroscopic mechanical forces are both large, potentially much larger than interatomic forces, and are directional and localized to an extent that differentiates them from other forms of energy input such as heat or light. As such, mechanical force represents a heretofore untapped approach to modulate catalyst geometry, with the potential to reversibly modulate catalyst geometry on the timescale of catalytic turnover or monomer enchainment. This project has addressed the fundamental challenges in material-to-molecule strain coupling associated with the development of a new class of mechanically responsive catalysts (mechanocatalysts) in which active organotransition metal catalysts are strategically embedded in a flexible polymer network such that application of external mechanical force (stretching or deformation) leads to modulation of catalyst geometry, and hence reactivity and selectivity. Our efforts during the tenure of this grant were directed toward the elucidation of force-reactivity relationships of elementary transformations that occur within the first coordination sphere of a transition metal complex employing stiff stilbene photoswitches tethered to a flexible bidentate phosphine ligand derived from MeOBiphep as molecular force probes which provide a range of compressive and extension forces to the coupled transition metal complex depending on the geometry of the stiff stilbene and length of the tethering chains. During the tenure of this grant, we have quantified the rate of C(sp 2 )-C(sp 2 ) reductive elimination from platinum(II) diaryl complexes containing bis(phosphine) force probe ligands as a function of mechanical force; compressive forces decreased the rate of reductive elimination whereas extension forces increased the rate relative to the strain-free MeOBiphep complex with a 3.4-fold change in rate over a ~290 pN range of restoring forces. In a similar manner, we have quantified the rate of oxidative addition of bromobenzene to low-ligated palladium(0) complexes containing force probe ligands as a function of mechanical force; compressive forces increase the rate of oxidative addition, whereas tensile forces decrease the rate with a ~6 fold change in rate across ~340 pN of force applied to the complexes. In both cases, experimental and computational analyses argue strongly against any significant force-induced perturbation of ground state geometry within the first coordination sphere of the reactant complexes. Rather, the force/rate behavior observed for these transformations across these ranges of forces is attributed to the coupling of force to the nuclear motion comprising the reaction coordinates for reductive elimination and oxidative addition. These results together inform the development of catalysts whose activity can be tuned by an external force that is adjusted within a catalytic cycle and suggest opportunities to experimentally map geometry changes associated with reactions in transition metal complexes and potential strategies for force-modulated catalysis.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2019

Mechanical-force-induced non-local collective ferroelastic switching in epitaxial lead-titanate thin films

Ferroelastic switching in ferroelectric/multiferroic oxides plays a crucial role in determining their dielectric, piezoelectric, and magnetoelectric properties. In thin films of these materials, however, substrate clamping is generally thought to limit the electric-field- or mechanical-force-driven responses to the local scale. Here, we report mechanical-force-induced large-area, non-local, collective ferroelastic domain switching in PbTiO 3 epitaxial thin films by tuning the misfit-strain to be near a phase boundary wherein c/a and a 1 / a 2 nanodomains coexist. Phenomenological models suggest that the collective, c-a-c-a ferroelastic switching arises from the small potential barrier between the degenerate domain structures, and the large anisotropy of a and c domains, which collectively generates much larger response and large-area domain propagation. Large-area, non-local response under small stimuli, unlike traditional local response to external field, provides an opportunity of unique response to local stimuli, which has potential for use in high-sensitivity pressure sensors and switches.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mechanical forces orchestrate the metabolism of the developing oilseed rape embryo

The initial free expansion of the embryo within a seed is at some point inhibited by its contact with the testa, resulting in its formation of folds and borders. Although less obvious, mechanical forces appear to trigger and accelerate seed maturation. However, the mechanistic basis for this effect remains unclear. Manipulation of the mechanical constraints affecting either the in vivo or in vitro growth of oilseed rape embryos was combined with analytical approaches, including magnetic resonance imaging and computer graphic reconstruction, immunolabelling, flow cytometry, transcriptomic, proteomic, lipidomic and metabolomic profiling. Our data implied that, in vivo, the imposition of mechanical restraints impeded the expansion of testa and endosperm, resulting in the embryo's deformation. An acceleration in embryonic development was implied by the cessation of cell proliferation and the stimulation of lipid and protein storage, characteristic of embryo maturation. The underlying molecular signature included elements of cell cycle control, reactive oxygen species metabolism and transcriptional reprogramming, along with allosteric control of glycolytic flux. Constricting the space allowed for the expansion of in vitro grown embryos induced a similar response. The conclusion is that the imposition of mechanical constraints over the growth of the developing oilseed rape embryo provides an important trigger for its maturation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Breaking a dative bond with mechanical forces

Bond breaking and forming are essential components of chemical reactions. Recently, the structure and formation of covalent bonds in single molecules have been studied by non-contact atomic force microscopy (AFM). Here, we report the details of a single dative bond breaking process using non-contact AFM. The dative bond between carbon monoxide and ferrous phthalocyanine was ruptured via mechanical forces applied by atomic force microscope tips; the process was quantitatively measured and characterized both experimentally and via quantum-based simulations. Our results show that the bond can be ruptured either by applying an attractive force of ~150 pN or by a repulsive force of ~220 pN with a significant contribution of shear forces, accompanied by changes of the spin state of the system. Our combined experimental and computational studies provide a deeper understanding of the chemical bond breaking process.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Quantum mechanical force field for hydrogen fluoride with explicit electronic polarization

The explicit polarization (X-Pol) theory is a fragment-based quantum chemical method that explicitly models the internal electronic polarization and intermolecular interactions of a chemical system. X-Pol theory provides a framework to construct a quantum mechanical force field, which we have extended to liquid hydrogen fluoride (HF) in this work. The parameterization, called XPHF, is built upon the same formalism introduced for the XP3P model of liquid water, which is based on the polarized molecular orbital (PMO) semiempirical quantum chemistry method and the dipole-preserving polarization consistent point charge model. We introduce a fluorine parameter set for PMO, and find good agreement for various gas-phase results of small HF clusters compared to experiments and ab initio calculations at the M06-2X/MG3S level of theory. In addition, the XPHF model shows reasonable agreement with experiments for a variety of structural and thermodynamic properties in the liquid state, including radial distribution functions, interaction energies, diffusion coefficients, and densities at various state points.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mapping mechanical force propagation through biomolecular complexes

In this paper, we employ single-molecule force spectroscopy with an atomic force microscope (AFM) and steered molecular dynamics (SMD) simulations to reveal force propagation pathways through a mechanically ultrastable multidomain cellulosome protein complex. We demonstrate a new combination of network-based correlation analysis supported by AFM directional pulling experiments, which allowed us to visualize stiff paths through the protein complex along which force is transmitted. Finally, the results implicate specific force-propagation routes nonparallel to the pulling axis that are advantageous for achieving high dissociation forces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Capturing Deuteration Effects in a Molecular Mechanics Force Field: Deuterated THF and the THF–Water Miscibility Gap

Deuteration is a common chemical modification used in conjunction with experiments such as neutron scattering, NMR, and Fourier-transform infrared for the study of molecular systems. Under the Born–Oppenheimer (BO) approximation, while the underlying potential energy surface remains unchanged by isotopic substitutions, isotopic substitution still alters intramolecular vibrations, which in turn may alter intermolecular interactions. Molecular mechanics (MM) force fields used in classical molecular dynamics simulations are assumed to represent local approximations of the BO potential energy surfaces, and hence, MD simulations using simple isotopic mass substitutions should capture BO-compatible isotope effects. However, standard MM force-field parameterizations do not directly fit to the local harmonic quantum mechanical (QM) Hessian that describes the BO surface, but rather to QM normal-modes and/or mass-dependent internal-coordinate derived distortion energies. In this study, using tetrahydrofuran (THF)–water mixtures as our model system, we show that not only does a simple mass-substitution approach fail to capture an experimentally characterized deuteration effect (the loss of the closed-loop miscibility gap associated with the complete deuteration of THF) but also it is necessary to generate new MM force-field parameters that correctly describe isotopic dependent vibrations to capture the experimental deuteration effect. We show that the origin of this failure is a result of using mass-dependent features to fit the THF MM force field, which unintentionally biases the bonded terms of the force field to represent only the isotopologue used during the original force-field parameterization. In addition, we make use of our isotopologue-corrected force field for D 8 THF to examine the molecular origins of the isotope-dependent loss of the THF–water miscibility gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces

Mechanical forces affect a myriad of processes, from bone growth to material fracture to touch-responsive robotics. While nano- to micro-Newton forces are prevalent at the microscopic scale, few methods have the nanoscopic size and signal stability to measure them in vivo or in situ. Here, we develop an optical force-sensing platform based on sub-25 nm NaYF 4 nanoparticles (NPs) doped with Yb 3+ , Er 3+ , and Mn 2+ . The lanthanides Yb 3+ and Er 3+ enable both photoluminescence and upconversion, while the energetically coupled d-metal Mn 2+ adds force tunability through its crystal field sensitivity. IN using a diamond anvil cell to exert up to 3.5 GPa pressure or ~10 μN force per particle, we track stress-induced spectral responses. The red (660 nm) to green (520, 540 nm) emission ratio varies linearly with pressure, yielding an observed color change from orange to red for α-NaYF 4 and from yellow–green to green for d-metal optimized β-NaYF 4 when illuminated in the near infrared. We record consistent readouts over multiple pressure cycles and hours of illumination. With the nanoscopic size, a dynamic range of 100 nN to 10 μN, and photostability, these nanoparticles lay the foundation for visualizing dynamic mechanical processes, such as stress propagation in materials and force signaling in organisms.

36 MATERIALS SCIENCE↗
DOE OSTI2014

A quantitative quantum-chemical analysis tool for the distribution of mechanical force in molecules

The promising field of mechanochemistry suffers from a general lack of understanding of the distribution and propagation of force in a stretched molecule, which limits its applicability up to the present day. In this article, we introduce the JEDI (Judgement of Energy DIstribution) analysis, which is the first quantum chemical method that provides a quantitative understanding of the distribution of mechanical stress energy among all degrees of freedom in a molecule. The method is carried out on the basis of static or dynamic calculations under the influence of an external force and makes use of a Hessian matrix in redundant internal coordinates (bond lengths, bond angles, and dihedral angles), so that all relevant degrees of freedom of a molecule are included and mechanochemical processes can be interpreted in a chemically intuitive way. The JEDI method is characterized by its modest computational effort, with the calculation of the Hessian being the rate-determining step, and delivers, except for the harmonic approximation, exact ab initio results. We apply the JEDI analysis to several example molecules in both static quantum chemical calculations and Born-Oppenheimer Molecular Dynamics simulations in which molecules are subject to an external force, thus studying not only the distribution and the propagation of strain in mechanically deformed systems, but also gaining valuable insights into the mechanochemically induced isomerization of trans-3,4-dimethylcyclobutene to trans,trans-2,4-hexadiene. The JEDI analysis can potentially be used in the discussion of sonochemical reactions, molecular motors, mechanophores, and photoswitches as well as in the development of molecular force probes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Evolution and forcing mechanisms of El Niño over the past 21,000 years

The El Niño Southern Oscillation (ENSO) is Earth’s dominant source of interannual climate variability, but its response to global warming remains highly uncertain1. To improve our understanding of ENSO’s sensitivity to external climate forcing, it is paramount to determine its past behaviour by using palaeoclimate data and model simulations. Palaeoclimate records show that ENSO has varied considerably since the Last Glacial Maximum (21,000 years ago), and some data sets predict a gradual intensification of ENSO over the past ~6,000 years. Other attempts to simulate the transient evolution of ENSO have relied on simplified models or snapshot experiments. In this work, we assess a series of transient Coupled General Circulation Model simulations forced by changes in greenhouse gasses, orbital forcing, the meltwater discharge and the ice-sheet history throughout the past 21,000 years. Consistent with most palaeo-ENSO reconstructions, our model simulates an orbitally induced strengthening of ENSO during the Holocene epoch, which is caused by increasing positive ocean–atmosphere feedbacks. During the early deglaciation, ENSO characteristics change drastically in response to meltwater discharges and the resulting changes in the Atlantic Meridional Overturning Circulation and equatorial annual cycle. Increasing deglacial atmospheric CO 2 concentrations tend to weaken ENSO, whereas retreating glacial ice sheets intensify ENSO. The complex evolution of forcings and ENSO feedbacks and the uncertainties in the reconstruction further highlight the challenge and opportunity for constraining future ENSO responses.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Culturing astrocytes on substrates that mimic brain tumors promotes enhanced mechanical forces

Highlights: • Human astrocytes increase traction forces of cells applied to the ECM in response to increased substrate stiffness. • Astrocytes apply intercellular stresses with noticeable increase in higher substrate stiffness. • Cell velocity decreases in human astrocytes in brain tumor like environment compared to normal brain environment. • Astrocytes mechanical strength and function could be potentially enhanced by increased stiffness of the microenvironment. Astrocytes are essential to brain homeostasis and their dysfunction can have devastating consequences on human quality of life. Such deleterious effects are generally due in part to changes that occur at the cellular level, which may be biochemical or biomechanical in nature. One biomechanical change that can occur is a change in tissue stiffness. Brain tumors are generally associated with increased brain tissue stiffness, but the impact increased tissue stiffness has on astrocyte biomechanical behavior is poorly understood. Therefore, in this study we cultured human astrocytes on flexible substrates with stiffness that mimicked the healthy human brain (1 kPa), meningioma (4 kPa), and glioma (11 kPa) and investigated astrocyte biomechanical behavior by measuring cell-substrate tractions, strain energies, cell-cell intercellular stresses, and cellular velocities. In general, tractions, intercellular stresses, and strain energy was observed to increase as a function of increased substrate stiffness, while cell velocities were observed to decrease with increased substrate stiffness. We believe this study will be of great importance to the fields of brain pathology and brain physiology.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Validated ligand geometries for macromolecular refinement restraints and molecular-mechanics force fields

In macromolecular structure refinement, the low observation-to-parameter ratio and the lack of high-resolution data are countered by using a priori information in the form of restraints. Having accurate geometries of the chemical entities in the sample is paramount for generating accurate chemical restraints and, therefore, accurate macromolecular structures. In particular, it is desirable to have accurate restraints for known and novel ligand entities. Quantum mechanics (QM) can minimize the energy of a ligand by adjusting its geometry, and these geometries can be used to generate restraints for macromolecular refinement. This article describes a library of approximately 37 000 small molecules extracted from the Chemical Component Dictionary in the Protein Data Bank and minimized by density-functional QM. The library includes restraint files for use in crystallography or cryo-EM refinement, along with files suitable for molecular-dynamics simulation. Because the geometries are validated using the Cambridge Structural Database, the restraints library provides users with both functional restraints and minimized geometries. This work also provides procedures for generating new and accurate restraints.

Amber↗
DOE OSTI2019

Plastic deformation and material transfer on steel gage blocks during low force mechanical probing

Contact probing of gaging surfaces is enabled throughout dimensional metrology. Probe tips such as ruby, sapphire, or diamond are commonly employed as styli for universal length measuring machines (ULMs) and coordinate measuring machines (CMMs) due to the hardness, durability, and wear resistance. Gaging surfaces of gage blocks are precision ground or lapped, with very low surface roughness to enable wringing. Damage or contamination of these surfaces can prevent wringing and lead to measurement error. Experimental investigations using a horizontal ULM and CMM have revealed that even at low force settings (≤0.16 N), probe materials such as ruby and sapphire can cause plastic deformation to hardened carbon chrome steel (such as AISI 52,100) gage block surfaces at the microscale, likely attributed to fretting-associated wear. Under some conditions, permanent transfer of material from the probe stylus to the gaging surface is possible. Results show irreversible changes and damage to gaging surfaces with repeated probe contact on a ULM and CMM. Optical microscopy, optical profilometry, and scanning electron microscopy (SEM) provide a semi-quantitative assessment of microscale plastic deformation and material transfer. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and Raman techniques validate chemical constituency of reference materials used (gage blocks and probes) and also identify makeup of deposits on gaging surfaces following probe contact.

42 ENGINEERING↗
DOE OSTI2026

Evaluations of Connectors, Inlets, and Adapters on Side-Load and Withstand Force

This report examines the mechanical forces that direct current fast charging (DCFC) electric vehicle supply equipment (EVSE) connectors and electric vehicle (EV) inlet ports experience during normal usage. As we witness the fast and growing variety of EVs, charge port locations, and bigger and more powerful EVSE configurations including the SAE J3400 North American Charging Standard (NACS), which has increased the use of adapters with J3400 and J1772 compatibility. These new conditions contribute to increased mechanical forces due to their size, weight and lever arm effect, which creates the need to study and compare these forces to the limits on UL2251 and IEC 62196-1 standards. This report focuses solely on high power DC charging EVSE connectors, EV inlets and adapters for the specific compatibility cases on J3400 with J1772. We first describe the details of the 100N and the 750N side-load evaluations as described in the standards, then present the data obtained by replicating these tests to finally go into more detail on the findings and our recommendations.

100N↗
DOE OSTI2016

Algorithms to automate gap-dependent integral tuning for the 2.8-meter long horizontal field undulator with a dynamic force compensation mechanism

A 2.8-meter long horizontal field prototype undulator with a dynamic force compensation mechanism has been developed and tested at the Advanced Photon Source (APS) at Argonne National Laboratory (Argonne). The magnetic tuning of the undulator integrals has been automated and accomplished by applying magnetic shims. A detailed description of the algorithms and performance is reported.

43 PARTICLE ACCELERATORS↗