Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ORIENTATION”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Improvement of aerosol activation/ice nucleation in a source-oriented WRF-Chem model to study a winter Storm in California

The source-oriented Weather Research and Forecasting chemistry (SOWC) model is modified to improve mixed-phase cloud parameterization by including aerosol aging processes (external mixture) in cloud activation/nucleation. The improved SOWC model is applied to investigate how aerosol mixing state influences cloud and ice formation and atmospheric optical properties during a winter storm. SOWC tracks 6-dimensional chemical variables (X, Z, Y, Size Bins, Source Types, Species) through an explicit simulation of atmospheric chemistry and physics. A new module is implemented into the enhanced SOWC model to simulate microphysics processes with all source-oriented hydrometeors (cloud, ice, rain, snow and graupel) by using the modified Morrison two-moment microphysics scheme. In this study, all aerosol source types can activate to form cloud droplets based on the Köhler theory, but the dust source type is the only source of ice nuclei (IN). Here, the Goddard shortwave and longwave radiation schemes are modified to use a new geometric optics method to estimate cloud optical properties by considering the chemistry components and the physical shape of each hydrometeor.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Circular orientation fluorescence emitter imaging (COFEI) of rotational motion of motor proteins

Single-molecule fluorescence polarization technique has been utilized to detect structural changes in biomolecules and intermolecular interactions. Here we developed a single-molecule fluorescence polarization measurement system, named circular orientation fluorescence emitter imaging (COFEI), in which a ring pattern of an acquired fluorescent image (COFEI image) represents an orientation of a polarization and a polarization factor. Rotation and pattern change of the COFEI image allow us to find changes in the polarization by eye and further values of the parameters of a polarization are determined by simple image analysis with high accuracy. We validated its potential applications of COFEI by three assays: 1) Detection of stepwise rotation of F{sub 1}-ATPase via single quantum nanorod attached to the rotary shaft γ; 2) Visualization of binding of fluorescent ATP analog to the catalytic subunit in F{sub 1}-ATPase; and 3) Association and dissociation of one head of dimeric kinesin-1 on the microtubule during its processive movement through single bifunctional fluorescent probes attached to the head. These results indicate that the COFEI provides us the advantages of the user-friendly measurement system and persuasive data presentations.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Fine-tuning the release of molecular guests from mesoporous silicas by controlling the orientation and mobility of surface phenyl substituents

Phenyl-functionalized mesoporous silica materials were used to explore the effect of non-covalent interactions on the release of Ibuprofen into simulated body fluid. Variations in orientation and conformational mobility of the surface phenyl groups were introduced by selecting different structural precursors: a rigid upright orientation was obtained using phenyl groups directly bound to surface Si atoms (Ph-MSN), mobile groups were produced by using ethylene linkers to connect phenyl groups to the surface (PhEt-MSN), and groups co-planar to the surface were obtained by synthesizing a phenylene-bridged periodic mesoporous organosilica (Ph-PMO). The Ibuprofen release profiles from these materials and non-functionalized mesoporous silica nanoparticles (MSN) were analyzed using an adsorption-diffusion model. The model provided kinetic and thermodynamic parameters that evidenced fundamental differences in drug-surface interactions between the materials. All phenyl-bearing materials show lower Ibuprofen initial release rates than bare MSN. The conformationally locked Ph-MSN and Ph-PMO have stronger interactions with the drug (negative ΔG of adsorption) than the flexible PhEt-MSN and bare MSN (positive ΔG of adsorption). These differences in strength of adsorption are consistent with differences between interaction geometries obtained from DFT calculations. B3LYP-D3-optimized models show that π-π interactions contribute more to drug adsorption than H-bonding with silanol groups. Here, the results suggest that the type and geometry of interactions control the kinetics and extent of drug release, and should therefore serve as a guide to design new drug delivery systems with precise release behaviors customized to any desired target.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effects of fiber dosage, loading orientation and stress on frequency response of enhanced Carbon Nano-Fiber Aggregates

Nanomaterial additives have been broadly used in cement and concrete-based sensors to measure the stress and strain in the structure. Most of the studies focused on measuring the resistivity of sensors with Direct Current (DC) or relatively low-frequency. Here in this work, the impedance responses of enhanced Carbon Nano-Fiber Aggregates (CNFAs) at different frequencies are rigorously studied and utilized as a tool for real-time structural health monitoring (SHM). The CNFA impedance measurements at different measurement frequencies provide an extra dimension (frequency dimension) to allow the characterization of different phenomena and multimodal measurements simultaneously. First, a comprehensive physical model is established to understand the frequency responses of the CNFA impedance. Second, COMSOL Multiphysics is used to simulate the frequency responses of the CNFA impedance, which provides more insights into the electric field and current density distribution. The impedance of CNFAs decreased with the increased dosage of carbon nanofibers (CNFs). Third, experimental studies are reported in detail. The electrical impedance variation (EZV) of the CNFA in parallel orientation is 151% higher than that of perpendicular orientation at the frequency of 2612 Hz and uniaxial compression stress of 4.65 MPa. The strain-EZV curve obtained from the response spectrum is linear for frequencies ranging from 98 Hz to 463.9 kHz. The strain-EZV curve for 5625 Hz has a linear fit with the gauge factor of 147.78. At 1000 Hz, the CNFA exhibited a repeatable behavior up to 9.35 MPa and detection limit up to the stress of 18.62 MPa.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Effects of build orientation and heat treatment on the evolution of microstructure and mechanical properties of alloy Mar-M-509 fabricated via laser powder bed fusion

We present the main results from an experimental investigation into the consequences of various microstructural features, created by laser powder bed fusion (LPBF) and subsequent heat treatments (HTs), in alloy Mar-M-509 on several aspects of plastic deformation including mechanical anisotropy and elongation-to-fracture (ETF). To ensure successful manufacturing of the alloy, porosity fraction and distribution are first characterized using micro X-ray computed tomography. Next, grain structure, crystallographic texture, and regions of recrystallization in the studied microstructures are measured using electron backscattered diffraction (EBSD). Lastly, chemistry, distribution, and morphological features of carbide phases are extracted using electron microscopy and X-ray diffraction. Strength in tension and compression are measured at room temperature for different initial microstructures created by variations in manufacturing conditions and sample orientations with respect to sample processing frame. While the strength of the alloy varies with sample orientation by approximately 30% in the as-built condition, the alloy is softer, more ductile, and approximately isotropic after HT. These results are discussed and critically compared with the data reported for the as-cast material. The alloy manufactured via LPBF is found to be significantly stronger and more ductile than the same alloy produced by casting. The interesting deformation behavior characteristics of the samples in different conditions are explained in terms of their microstructures. EBSD measurements reveal evolution from columnar grains along the build direction favoring a moderately strong <001> fiber texture in the as-built material to equiaxed grains favoring the {110}<001> Goss texture component after subsequent HTs. The major change in grain structure and texture is a result of recrystallization. While carbide phases precipitate primarily at dendrite and cellular interfaces in the as-built material, these phases are both intra-and inter-granular within the HT materials and coarsen with HT duration. These microstructural observations formed bases to rationalize the observed mechanical behavior of the alloy. With this being said, tailoring the alloy performance characteristics with HTs is reported on.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of neighboring grain orientation on strain localization in slip bands in HCP materials

Particularly in plastically anisotropic crystals, such as hexagonal close packed (HCP) materials, plastic deformation is realized by slip acting in the small volumes within individual crystals. Here we extend a full field fast Fourier transform (FFT)-based elasto-viscoplastic formulation to simulate the development of a single slip band on either prismatic or basal planes spanning a crystal. Calculations of the strain and stress fields induced locally within the band and parent crystal, and ahead of the band/grain boundary junction in the neighboring crystal are analyzed as the slip band intensifies under increasing applied strain. We report a substantial influence of the crystallographic orientation of the nearest neighboring grain on the rate of slip band localization. Performing the analysis on two materials, CP-Ti and Mg, indicates that the strength of the material affects the rate of localization, with stronger materials tending to localize more easily. A slip band tip stress-based criterion is proposed for identifying the nearest neighbor orientations in which slip band transmission is possible and the likely slip system for which it occurs. This indicator is validated against experimental studies on commercially pure Ti, an Mg–Y alloy, and Ti–6Al–4V. Finally, we show that for low GB misorientations, the slip band is likely to transmit into another slip band of the same type in the neighbor grain, while for high GB misorientations, it is likely to transmit into one of a different type or to not transmit at all.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Determination of the relative orientation between 15 N- 1 H dipolar coupling and 1 H chemical shift anisotropy tensors under fast MAS solid-state NMR

Here, in this work, we have proposed a proton-detected three-dimensional (3D) 15 N- 1 H dipolar coupling (DIP)/ 1 H chemical shift anisotropy (CSA)/ 1 H chemical shift (CS) correlation experiment to measure the relative orientation between the 15 N- 1 H dipolar coupling and the 1 H CSA tensors under fast magic angle spinning (MAS) solid-state NMR. In the 3D correlation experiment, the 15 N- 1 H dipolar coupling and 1 H CSA tensors are recoupled using our recently developed windowless C-symmetry-based $C3^{1}_{3}$-ROCSA (recoupling of chemical shift anisotropy) DIPSHIFT and $C3^{1}_{3}$-ROCSA pulse-based methods, respectively. The 2D 15 N- 1 H DIP/ 1 H CSA powder lineshapes extracted using the proposed 3D correlation method are shown to be sensitive to the sign and asymmetry of the 1 H CSA tensor, a feature that allows the determination of the relative orientation between the two correlating tensors with improved accuracy. The experimental method developed in this study is demonstrated on a powdered U- 15 N L-Histidine.HCl·H 2 O sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Orientation relationships of phase transformation in α-Al12Mn3Si pseudomorphs after plate-like Al6Mn precipitate in an AA3004 Al-Mn based alloy

Highlights: • The phase transformation in the plate-like precipitates was investigated by TEM. • The shape of a plate-like Al{sub 6}Mn was kept after transforming to the α-Al{sub 12}Mn{sub 3}Si. • Pseudomorph in metal materials has been found out. - Abstract: The phase transformation in the plate-like precipitates of Al{sub 6}Mn in an AA3004 Al-Mn based alloy, which was prepared by a chemical extraction technique, was investigated using transmission electron microscopy. The boiling-phenol method observed the entire range of possible shapes of the precipitates and the habit planes of the plate-like Al{sub 6}Mn were <001> in the sheet plane and <110> on its edges. The two orientation relationships between Al{sub 6}Mn and α-Al{sub 12}Mn{sub 3}Si after the phase transformation is observed to be [00 1-bar ]{sub 6}//[02 3-bar ]{sub α} and (130){sub 6}//(5 3-bar 2){sub α} and [00 1-bar ]{sub 6}//[1 5-bar 2]{sub α} and (200){sub 6}//(311){sub α} (particles 1 and 2) (the suffixes 6 and α indicate zone axises or lattice planes of Al{sub 6}Mn and α-Al{sub 12}Mn{sub 3}Si phases, respectively). The lattice misfits in these orientation relationships were observed to be − 1.4% and 1.0%, respectively. Additionally, the thickness of the plate-like Al{sub 6}Mn was kept constant after transforming into the α-Al{sub 12}Mn{sub 3}Si phase. Further, we did not observe any low index planes of the α-Al{sub 12}Mn{sub 3}Si parallel to the (001) plane of the Al{sub 6}Mn, which means that the outlines of α-Al{sub 12}Mn{sub 3}Si were constrained by the original shape of Al{sub 6}Mn, i.e., the transformed α-Al{sub 12}Mn{sub 3}Si may be considered as a pseudomorph after Al{sub 6}Mn.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effects of thickness and orientation on the small scale fracture behaviour of additively manufactured Ti-6Al-4V

Highlights: • Miniaturized specimens successfully additively manufactured via SLM and SEBM. • Small-scale tensile testing of specimens to capture orientation/thickness effect. • Tomography characterization of defects. • Location dependence of fracture behavior. - Abstract: The effects of sample location, orientation, and thickness on the microstructure and resulting tensile properties of miniature SLM and SEBM AM samples of Ti-6Al-4V has been determined. Microstructure and mechanical property variations in the miniature samples are shown to be related to build orientation and also partly to specimen thickness and position within the build chamber. The present work is our initial attempt to develop a systematic approach for characterization of the microstructure (including defects via tomography) and mechanical properties on miniature AM test specimens that can also be used to reveal issues related to process stability (e.g. fluctuations in build conditions). The discussion is also included regarding their relevance to miniature samples that can be manufactured along with parts, excised from larger samples, and/or excised from actual manufactured components.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Secondary recrystallization behavior in strip-cast grain-oriented silicon steel processed by isothermal secondary annealing

Highlights: • Abnormal grain growth was successfully developed after annealing at 1025 °C for 15 min. • The formation mechanism of the Goss and {110}<227> secondary grains was elucidated. • Retention of matrix grain colonies in the interior or at the grain boundaries of secondary grains was explained. - Abstract: The primary annealed sheets of strip-cast grain-oriented silicon steel were isothermally secondary annealed for 15 min under 100% H{sub 2} atmosphere. The microstructure and crystallographic orientation at different annealing temperatures were characterized and the secondary recrystallization behavior was elucidated. It was observed that relatively complete abnormal grain growth occurred at 1025 °C. Incomplete abnormal grain growth developed when the temperature was lower than 1025 °C, and normal grain growth occurred when the temperature was higher than 1025 °C. During the abnormal grain growth, both of the Goss and {110}<227> grains developed because of the rapid decrease of the inhibiting force and the limited annealing time. Considering the high energy boundary (HE), coincidence site lattice boundary (CSL) and solid-state wetting (SSW) models for abnormal grain growth, the first one explained the development of the Goss and {110}<227> grains. Another result was that several matrix grain colonies were observed in the interior or at the boundaries of secondary grains after abnormal grain growth. The grains at the periphery of these colonies showed a large fraction of high energy boundaries (20–45° misorientation) with the surrounding secondary grain and similar grain size with the unconsumed matrix grains. Therefore, these colonies were expected to be consumed by prolonging the annealing time and thus the limited annealing time was responsible for their occurrence. A possible explanation for the dominated high energy boundaries instead of low energy boundaries at the periphery of these colonies was proposed. All of these behaviors promoted the understanding of abnormal grain growth.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of annealing after strip casting on microstructure, precipitates and texture in non-oriented silicon steel produced by twin-roll strip casting

Highlights: • Non-oriented silicon steel with superior magnetic properties was produced by twin-roll strip casting. • The effect of annealing after strip casting on microstructure, precipitates and texture was investigated. • Role of precipitates in microstructure and texture evolution along the entire route was explored. • High magnetic induction and strong λ-fiber texture was obtained by optimizing strip annealing process. - Abstract: A 3.1 mm thick non-oriented Fe-1.0% Si steel as-cast strip was produced by twin-roll strip casting. Samples with/without strip annealing were cold rolled to 0.5 mm and then annealed. The development of microstructure, precipitate and texture was characterized along the entire processing route. It was found that annealing after strip casting had a minor influence on the average grain size and texture of the as-cast strip. A large number of particles precipitated and coarsened during the strip annealing process. Meanwhile, precipitates hindered dislocation slip and crystal rotation such that more significant in-grain shear bands were formed in cold rolled sheets. During recrystallization annealing process, the newly formed fine precipitates in directly cold-rolled sheets consumed stored strain energy and also hindered grain growth. But the initial precipitates in the annealed strip grew further and the effect of pinning of dislocations and grain boundary was lost. Therefore, annealed sheets with strip annealing process showed homogeneous equiaxed grains and the recrystallization texture was characterized by strong λ-fiber texture, which led to high permeability.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Build orientation, surface roughness, and scan path influence on the microstructure, mechanical properties, and flexural fatigue behavior of Ti–6Al–4V fabricated by electron beam melting

In the present work, microstructure and fatigue behavior of Electron Beam Melted (EBM) Ti–6Al–4V have been systematically studied. Fatigue behavior was investigated using four-point bend tests of rectangular bars with internal features fabricated with different build orientations, scan paths, and surface conditions. Microstructural variations were evaluated by optical microscopy and Vickers micro-hardness indentations, both of which were found to be consistent throughout the build and within ranges reported in the literature. The fatigue performance of the EBM material was comparable to wrought Ti–6Al–4V when the loading direction was parallel to the build direction, but severely limited when loaded perpendicular to the build direction or if surface roughness defects were present. Scanning electron microscopy and interrupted fatigue tests were utilized to characterize fracture surfaces, failure mechanisms, crack initiation, and propagation behavior. Crack initiation sites in the vertically-oriented specimens were identified to be melt-related defects formed by insufficient melting.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Passive heat removal in horizontally oriented micro-HTGRs

There are novel, horizontally oriented high-temperature gas-cooled micro-reactor (HTGR) designs under consideration because of their portability, simplicity, and reliable operation. These features of the micro-HTGR design can meet the fission battery attributes, such as economic, standardize, installed, unattended and reliable. Although there have been HTGR related safety studies, micro-HTGRs when horizontally oriented are expected to exhibit significantly different thermal physics. During the unavailability of helium circulation, the internal reactor core is designed to cool by block-to-block conduction and radiation, and the reactor vessel surface is cooled by the ambient air. This scenario is anticipated during the transport of the micro-HTGR in a shipping container. The conduction and radiation between the prismatic micro-HTGR blocks in the core can be influenced by variances in the thermal contacts. This work investigated the conduction within a simulated horizontal HTGR core. An experimental setup was used to validate a numerical model. The experimental setup consisted of a hexagonal assembly with scaled prismatic blocks placed within a high-temperature vacuum environment. The gaps between the blocks were well controlled and monitored. The experimental setup was designed in such a way that the temperature variation in the axial direction was minimal, such that the experiment could be observed as a 2D (r, ) heat transfer problem. The pressurized tube was equipped with Infra-Red (IR) transparent windows, and an IR camera was used to capture the spatio-temporal temperature evolution in the hexagonal block assembly during the cooldown experiments. The experimental scenario was computationally modeled with a finite element analysis (FEA) program. Once validated, the computational model was used to investigate the impact of gap conductance on overall decay heat removal. Using a conservative estimate for gap conductance value (100 W/m 2 -K) between the prismatic blocks, there is a negligible increase in temperature observed during decay heat generation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Highly Oriented Organic Ferroelectric Films with Single-Crystal-Level Properties from Restrained Crystallization

Device applications often require thin film growth with quasi-two-dimensional morphology and crystallization which are not always compatible. In this work, we exploit the method of low-temperature deposition followed by restrained crystallization (LDRC) in the growth of crystalline organic molecular thin films, which tend to grow three-dimensionally with random orientations. We demonstrate that, for 2-methylbenzimidazole (MBI), a molecular ferroelectric that tends to crystalize in spherulites, the quasi-two-dimensional films can be grown using LDRC with highly oriented polar axes and single-crystal-level ferroelectric properties. The crystallization process was shown to occur during the post-deposition annealing process using the in situ electrical measurements. The limited diffusion, low nucleation density, and low activation energy was found critical for the formation of the plate-shaped quasi-two-dimensional films. These results mark an important step in elucidating the LDRC as an effective and general approach for fabricating films with balanced crystallinity and morphology which are critical for applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hydrogen Storage Performance of Preferentially Oriented Mg/rGO Hybrids

Chemical interactions on the surface of a functional nanoparticle are closely related to its crystal facets, which can regulate the corresponding energy storage properties like hydrogen absorption. In this study, we reported a one-step growth of magnesium (Mg) particles with both close- and nonclose-packed facets, that is, {0001} and {$2\overline{116}$} planes, on atomically thin reduced graphene oxide (rGO). The detailed microstructures of Mg/rGO hybrids were revealed by X-ray diffraction, selected-area electron diffraction, high-resolution transmission electron microscopy, and fast Fourier transform analysis. Hydrogen storage performance of Mg/rGO hybrids with different orientations varies: Mg with preferential high-index {$2\overline{116}$} crystal surface shows remarkably increased hydrogen absorption up to 6.2 wt % compared with the system exposing no preferentially oriented crystal surfaces showing inferior performance of 5.1 wt % within the first 2 h. First-principles calculations revealed improved hydrogen sorption properties on the {$2\overline{116}$} surface with a lower hydrogen dissociation energy barrier and higher stability of hydrogen atoms than those on the {0001} basal plane, supporting the hydrogen uptake experiment. In addition, the hydrogen penetration energy barrier is found to be much lower than that of {0001} because of low surface atom packing density, which might be the most critical process to the hydrogenation kinetics. Here, the experimental and calculation results present a new handle for regulating the hydrogen storage of metal hydrides by controlled Mg facets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

Two-dimensional (2D) halide perovskites exhibit excellent potential for optoelectronics because of their outstanding physical properties and structural diversity. White-light emission is one property of 2D perovskites that originates from self-trapped excitons (STE) in the highly distorted structures. The so-called (110)-oriented 2D perovskites are generally distorted and believed to be good candidates for white-light emitting devices. Here, we report (110)-oriented 2D perovskites, C 4 N 2 H 12 PbX 4 (X = I, Br, Cl), templated by the small cyclic diammonium cation, 3-aminopyrrolidinium (3APr). Structural characterization by single-crystal X-ray diffraction reveals that the distortion of the inorganic part of the structures is influenced by the stereochemical conformation of the cation between the perovskite layers. The experimental bandgaps follow the trend I < Br < Cl (2.56 eV, 3.29 eV, 3.85 eV, respectively). Density functional theory calculations reveal a weak but significant electronic band dispersion along the stacking axis, suggesting a non-negligible interlayer electronic coupling caused by the short proximity of adjacent inorganic layers. The high level of distortion results in the emergence of white-light emission, rarely seen in iodide perovskites, as well as the bromide and chloride isostructural analogues, which provides perfect platform to compare the broad emission mechanism for all three halides. The bromide and chloride perovskites show longer lifetimes and higher color rendering index (CRI) (83 and 85), relevant to solid-state lighting. Lastly, temperature-dependent PL measurements confirm that the broad emission comes from different STE mechanism for different halides, with the peak broadening persisting even at low temperature for the chloride compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Orientational Disorder of NH3 in Hexammine Magnesium Borohydride

Hexammine magnesium borohydride, Mg(NH3)6(BH4)2, consists of adducted NH3 molecules locked in a matrix of Mg cations and borohydride anions. It is a candidate material for hydrogen storage, with 16.8 wt % hydrogen stored in both the NH3 and borohydride anions. It may also be of interest as an Mg2+-conducting electrolyte in solid-state batteries. Its crystal structure has, until now, eluded a proper structural solution due to ambiguity regarding the NH3 position and behavior. In this work, we show using synchrotron X-ray diffraction that the room-temperature structure can be solved only with a model assuming the orientational disorder of ammonia molecules within the crystal structure. Cooling the sample to 120 K yields additional Bragg peaks, which can be solved only with a unit cell expansion consistent with the freezing of the orientational freedom of ammonia molecules. Using this insight from the structure solution, we performed a full assignment of the vibrational modes in the room-temperature infrared spectrum.

08 HYDROGEN↗
DOE OSTI2017

Extent of Surface Force Additivity on Chemically Heterogeneous Substrates at Varied Orientations

Surface interactions between chemically mixed surfaces, as well as those among dissolved biomolecules, comprise distinct contributions from polar and hydrophobic moieties. These contributions are often context dependent. Approximate compliance to the Cassie additivity equation for the wetting free energies on mixed surfaces in water is, however, indicative of similarly additive forces between individual surface elements, suggesting a quadratic interpolation model for total force from the forces between pure surfaces. We use molecular dynamics/umbrella sampling simulations of parallel and nonparallel mixed surfaces with demonstrable Cassie-like behavior to verify how well the total surface force between the heterogeneous, molecularly rough surfaces can be approximated as a combination of forces among the homogeneous ones. When accounting for dissimilar distances of approach between functional groups of different types, our results for graphene surfaces with mixed methyl and nitrile coating show such a superposition to provide a reasonable first order approximation of interactions between the platelets. Deviations from additivity are more prominent in parallel-plate configurations, at high content of hydrophobic groups, and small separations. The inclusion of water polarizability does not visibly alter the observed behavior regardless of platelet orientations. The outcome of this study determines the necessary molecular conditions for observing force additivity that emphasize the context dependence of hydrophobic interaction in the presence of polar groups. This notion provides guidelines for the syntheses of new, chemically heterogeneous materials with tailored function-oriented properties in aqueous media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗