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267 records · Page 15

Evaluating the Impact of Redox Potential on the Corrosion of Q125, 316L, and C276 Steel in Low-Temperature Geothermal Systems

Time series experiments were used to explore the fluid redox impact on the corrosion of Q125, 316L, and C276 steels in low-ionic-strength and neutral water at temperature and pressure conditions associated with low-temperature geothermal systems. After exposing polished samples of each steel grade to an oxidizing (H2O2) and a reducing (Zn-doped) fluid for intervals of 24 h, 1 week, and 6 weeks, the atomic force microscopy results revealed general corrosion for Q125, while 316L and C276 exhibited pitting, crevice expansion, and edge attack corrosion. Secondary depositional features are frequently found as topographic highs, adjacent to pitting corrosion. These features may be identified as there is a very strong spatial correlation between the height retrace and phase retrace surface maps. All steels became progressively rougher over time after exposure to both fluids, while the corrosion rates were more complex. Samples exposed to the reducing fluid experienced an increase in the corrosion rate over time, while C276 and 316L experienced a decrease in the corrosion rate. Finally, a novel data validation technique was developed to address the intrinsic scalability of corrosion. The results indicate that the AFM scan area does not affect the measured surface roughness over nearly three orders of magnitude.

Bowman, Samuel (ORCID:000000021510174X)↗

Impacts of Focused Ion Beam Processing on the Fabrication of Nanoscale Functionalized Probes

Herein, we examine the impact of Ga + ion kinetic energy and the target material type on the extent of ion implantation and structural damage in atomic force microscopy probes made of Al 2 O 3 and ZnO manufactured by focused ion beam (FIB) using scanning transmission electron microscopy and energy-dispersive X-ray mapping. Penetration of Ga into the Al 2 O 3 lattice induced structural distortions and amorphization. For ZnO probes, Ga is uniformly dispersed across the surface, resulting in the formation of distinct clusters. Atom probe tomography further validates the Ga distributions in Al 2 O 3 and ZnO nanoprobes. Complementary Monte Carlo simulations with the transport of ions in the matter program indicated that the introduction of Ga + prompts the generation of cation and anion vacancies, an occurrence more pronounced in Al 2 O 3 compared to ZnO. In conclusion, this study not only enriches the knowledge of ion-matter interactions, but also serves as a practical guide for the fabrication of nanoscale functionalized AFM probes.

Al2O3↗

Exploring Domain-Wall Pinning in Ferroelectrics via Automated High-Throughput Atomic Force Microscopy

Domain-wall dynamics in ferroelectric materials are strongly position-dependent, since each polar interface is locked into a unique local microstructure. This necessitates spatially resolved studies of wall pinning using scanning-probe microscopy techniques. The pinning centers and pre-existing domain walls are usually sparse within the image plane, precluding the use of dense hyperspectral imaging modes and requiring time-consuming human experimentation. Here, a large-area epitaxial PbTiO 3 film on cubic KTaO 3 was investigated to quantify the electric-field-driven dynamics of the polar–strain domain structures using ML-controlled automated piezoresponse force microscopy. Analysis of 1500 switching events reveals that domain-wall displacement depends not only on field parameters but also on the local ferroelectric–ferroelastic configuration. For example, twin boundaries in polydomains regions, like a 1 – /c+ ∥ a 2 – /c – , stay pinned up to a certain level of bias magnitude and change only marginally as the bias increases from 20 to 30 V, whereas single-variant boundaries, like the a 2 + /c + ∥ a 2 – /c – stack, are already activated at 20 V. These statistics on the possible ferroelectric and ferroelastic wall orientations, together with the automated high-throughput AFM workflow, can be distilled into a predictive map that links domain configurations to pulse parameters. Here, this microstructure-specific rule set forms the foundation for the design of ferroelectric memories.

automated scanning probe microscopy↗

Nanoscale Control of the Metal–Insulator Transition at LaAlO 3 /KTaO 3 Interfaces

Recent reports of superconductivity at KTaO 3 (KTO) (110) and (111) interfaces have sparked intense interest due to the relatively high critical temperature as well as other properties that distinguish this system from the more extensively studied SrTiO 3 (STO)-based heterostructures. Here, we report the reconfigurable creation of conducting structures at intrinsically insulating LaAlO 3 / KTO(110) and (111) interfaces. Devices are created using two distinct methods previously developed for STO-based heterostruc-tures: (1) conductive atomic-force microscopy lithography and (2) ultralow-voltage electron-beam lithography. At low temperatures, KTO(110)-based devices show superconductivity that is tunable by an applied back gate. A one-dimensional nanowire device shows single-electron-transistor (SET) behavior. A KTO(111)-based device is metallic but does not become superconducting. Finally, these reconfigurable methods of creating nanoscale devices in KTO-based heterostructures offer new avenues for investigating mechanisms of superconductivity as well as development of quantum devices that incorporate strong spin-orbit interactions, superconducting behavior, and nanoscale dimensions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of chloride ingress on self-healing recovery of smart cementitious composite incorporating crystalline admixture and MgO expansive agent

Highlights: • Crack closure under wet/dry cycles in chloride solution is higher than the one in distilled water. • Element analysis shows that calcium is vital for crack healing either in water or chloride solution. • AFm is consumed by chloride ion to form Fs, and Fs were decomposed to AH{sub 3} by carbonation. • Soluble reactive silica reacts with calcium hydrate to form C-S-H gel to heal concrete cracks. • Expansion of magnesium hydroxide facilitates crack self-healing by interconnected network. In this study, the effect of chloride environment containing various concentrations of chloride ion (Cl{sup −}) on self-healing performance of pre-cracked cementitious composite containing crystalline admixture (CA) and MgO expansive agent (MEA) was investigated under wet-dry cycles in chloride solutions. The results revealed that the Cl{sup −} changed the mineralogy of self-healing products, and consequently, affected the crack closure ratio and mechanical strength recovery. When self-healing occurred in distilled water, a large amount of ettringite (AFt) were detected, whereas in Cl{sup −} solution, monosulfate (AFm) was consumed by Cl{sup −} to form Friedel's salt (Fs), and then the Fs was decomposed to Al(OH){sub 3}(AH{sub 3}) due to carbonation. During the multiphase conversion process, hydroxide (OH{sup −}) was released into crack solution, therefore the dissolved carbon dioxide (CO{sub 2}) concentration was increased. The carbonation of the crystals formed in cracks was accelerated with the volume expansion, which achieved rapid crack sealing but contributed little to the mechanical performance recovery.

36 MATERIALS SCIENCE↗

Inducing Circularly Polarized Single-Photon Emission via Chiral-Induced Spin Selectivity

One of the central aims of the field of spintronics is the control of individual electron spins to effectively manage the transmission of quantized data. One well-known mechanism for controlling electronic spin transport is the chiral-induced spin-selectivity (CISS) effect in which a helical nanostructure imparts a preferential spin orientation on the electronic transport. One potential application of the CISS effect is as a transduction pathway between electronic spin and circularly polarized light within nonreciprocal photonic devices. Here in this work, we identify and quantify the degree of chiral-induced spin-selective electronic transport in helical polyaniline films using magnetoconductive atomic force microscopy (mcAFM). We then induce circularly polarized quantum light emission from CdSe/CdS core/shell quantum dots placed on these films, demonstrating a degree of circular polarization of up to ~21%. Utilizing time-resolved photoluminescence microscopy, we measure the radiative lifetime difference associated with left- and right-handed circular polarizations of single emitters. These lifetime differences, in combination with Kelvin probe mapping of the variation of surface potential with magnetization of the substrate, help establish an energy level diagram describing the spin-dependent transport pathways that enable the circularly polarized photoluminescence.

36 MATERIALS SCIENCE↗

Autogenous formation and smart behaviors of nitrite- and nitrate-intercalated layered double hydroxides (LDHs) in Portland cement-metakaolin-dolomite blends

In this work, the influence of sodium nitrite (NaNO{sub 2}) and sodium nitrate (NaNO{sub 3}) corrosion inhibitors on the composition, structure, and chloride binding behaviors of layered double hydroxides (LDHs) formed in ternary ordinary Portland cement-metakaolin-dolomite (OPC-MK-DM) systems is studied. The results show that the nitrite and nitrate anions are preferably intercalated in the CaAl LDHs (AFm phases), but not in the MgAl LDHs (hydrotalcite-type phases) due to its limited formation in these ternary cementitious systems cured at ambient temperature. The autogenously formed nitrate- and nitrite-AFm phases are decomposed upon chloride exposure accompanied by Friedel's salts formation, potentially releasing corrosion inhibitive ions to the pore solution in a progressive manner. The NaNO{sub 2} and NaNO{sub 3} incorporation in ternary OPC-MK-DM binders marginally lowers chloride binding capacity but reduces its penetration resistance mainly due to pore coarsening. Nevertheless, a strong linear correlation can be established between the water-soluble and total chloride contents in ternary OPC-MK-DM systems, regardless of OPC replacement level and corrosion inhibitor incorporation.

36 MATERIALS SCIENCE↗

Machine learning-driven descriptions of protein dynamics at solid-liquid interfaces

This chapter has described how ML has enabled quantitative analysis of HS-AFM data to discover the physical phenomena governing protein dynamics and ordering at solid-liquid interfaces. The research detailed in this chapter modeled the rotation models of protein nanorods, the discovery of which would otherwise not be possible. By tracking the trajectories of individual protein rods from frame to frame, it was possible to model Brownian type motion and behaviors and Levy-flight dynamics that had not previously been shown. We also described the application of the Python package AtomAI, which has been developed specifically to analyze and extract physical phenomena, providing exemplar code for training an ensemble of deep neural networks to produce the semantic segmentation of AFM data and functions for encoding and decoding local environments. We last described a combinatorial approach to analyze very noisy data with a densely covered substrate where the emergence of order for the protein liquid crystals could be elucidated. By combining the methods from Case 1 and 2, it was possible to obtain the center of mass and angle for each rod in the images and track the assembly of the rods over time into a 2D liquid crystal array on the surface of mica.

protein dynamics, solid-liquid interfaces, atomic ↗

Nanoscale control of LaAlO 3 /SrTiO 3 conductance beyond the polar catastrophe

Conductive atomic force microscope (c-AFM) lithography can be utilized to create a wide range of LaAlO 3 /SrTiO 3 (LAO/STO)-based nanoelectronic devices in a reconfigurable manner. Experiments were generally performed with intrinsically insulating LAO/STO heterostructures, with LAO thickness less than the critical value at which a polar catastrophe takes place [<4 unit cell (u.c.)]. Here, we use inductively coupled plasma reactive ion etching (ICPRIE) to fabricate c-AFM “canvases” on intrinsically conducting LAO/STO samples with ≥4 u.c. LAO. We observe that its interfacial two-dimensional electron gas (2DEG) can be pinched off and then switched back on by c-AFM lithography. Nanowires created with initially conductive LAO/STO interfaces have an order-of-magnitude longer lifetime in ambient conditions, when compared to an identically created 3.4 u.c. LAO/STO nanowire. We also demonstrate key nanoscale properties such as ballistic transport in a quasi-one-dimensional electron waveguide at a 5 u.c. LAO/STO interface. This approach frees c-AFM-written nanodevice designs from time constraints in air associated with <4 u.c. LAO/STO heterostructures.

36 MATERIALS SCIENCE↗

Interfacial-Strain-Controlled Ferroelectricity in Self-Assembled BiFeO 3 Nanostructures

Self-assembled BiFeO 3 -CoFe 2 O 4 (BFO-CFO) vertically aligned nanocomposites are promising for logic, memory, and multiferroic applications, primarily due to the tunability enabled by strain engineering at the prodigious epitaxial vertical interfaces. However, local investigations directly revealing functional properties in the vicinity of such critical interfaces are often hampered by the size, geometry, microstructure, and concomitant experimental artifacts. Ferroelectric switching in the presence of lateral distributions of vertical strain thus remains relatively unexplored, with broader implications for all strain-engineered functional devices. Additionally, by implementing tomographic atomic force microscopy, 3D domain orientation mapping, and spatially-resolved ferroelectric switching movies, local tensile strain significantly impacts the ferroelectric switching, principally by retarding domain nucleation in the BFO nearest to the vertically epitaxial tensile-strained interfaces. The relaxed centers of the BFO pillars become preferred domain nucleation and growth sites for low biases, with up to an order of magnitude change in the edge:center switching ratio for high biases. The new, multi-dimensional imaging approach—and its corresponding insights especially for directly strained interface effects on local properties—thereby advances the fundamental understanding of polarization switching and provides design principles for optimizing functional response in confined nanoferroic systems.

36 MATERIALS SCIENCE↗

Influence of pH on chloride binding isotherms for cement paste and its components

In this paper, chloride (Cl{sup −}) binding isotherms are developed for cement hydration compounds, specifically, calcium-silicate-hydrates (CSH) and AFm phases including mono-sulfate aluminate, hydroxy-AFm, monocarbonate-AFm, and hemicarbonate-AFm, in simulated concrete pore solutions to account for the effect of pH and the presence of other ions. pH and the presence of other ions have a strong influence on the Cl{sup −} binding capacity of cement compounds, which have not been taken into consideration in previous research. A novel experimental technique is developed to characterize the binding capacity from very low (1 mM) to very high concentrations (5 M). To overcome the existing challenges of measuring both low and high Cl{sup −} concentrations without significant dilution and in the presence of SO{sub 4}{sup 2−} and OH{sup −} ions, a potentiometric method was used. The amorphous CSH in the hydrated cement paste; thus, the heterogeneity of the hydrated components of the cement paste was also quantified and accounted for in this study.

36 MATERIALS SCIENCE↗

Light-Induced Transformation of Virus-Like Particles on TiO 2

Titanium dioxide (TiO 2 ) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO 2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO 2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO 2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO 2 surface. The in situ GISAXS measurements under an N 2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

36 MATERIALS SCIENCE↗

Synthesis and characterization of electron beam irradiation-induced damage in polycrystalline metal thin films

High-energy physics research, industrial sterilizing, and material processing depend extensively on electron beam accelerators. Exit windows are crucial components of such electron accelerator systems, maintaining vacuum integrity inside the machine while providing mechanical strength, thermal stability, and radiation resistance at the beam-target interface. In this study, thin metallic films of Ni, Ti, Cr, and V were explored for use in electron beam exit windows, and their properties were compared with the properties of their bulk counterparts. Simulation results of metal foils predicted Ti to exhibit less beam power dissipation compared to Ni. However, Ni possesses superior mechanical and structural properties compared to Ti. The performance of these films under electron beam irradiation was examined by depositing thin layers of these films on silicon and metallic substrates using magnetron sputtering and exposing them to e-beam irradiation in a controlled setup. The deposited films were subjected to a dose of approximately 66 kGy at a beam energy of 10 MeV and characterized prior to and postexposure to the beam using field emission scanning electron microscopy, atomic force microscopy, x-ray diffraction (XRD), and nanoindentation. Particular emphasis was given to characteristics like the grain structure, surface morphology, dislocation density, and hardness. XRD patterns revealed irradiation-induced changes in peak intensities, while the crystallinity remained largely unchanged. Nanoindentation results showed that the pristine and irradiated Ti and Ni films were twice as hard when compared to bulk Ti and Ni samples, regardless of the substrate type used (Si or bulk Ti, or Ni). These results emphasize the superior mechanical properties of thin metal films compared to their bulk counterparts. In conclusion, this study advances the optimization of thin film materials for robust and efficient e-beam applications, ensuring improved durability and operational reliability.

AFM↗

Multiscale water drop contact angles at selected silica surfaces

In this paper, multiscale advancing contact angles for glycerol/water drops at silica surfaces are reported for millidrops, submicron-drops, and nanodrops. Selected silica surfaces were muscovite, silicon, and talc. The contact angles for millidrops (1–2 mm) were determined by the traditional sessile drop technique. For submicron-drops (0.1–1.0 μm), a hollow tip Atomic Force Microscope (AFM) procedure was used. The contact angles for nanodrops (~7 nm) were examined from Molecular Dynamics (MD) simulation. The results were compared to evaluate the effect of drop size on the contact angle. In the case of the hydrophobic talc surface, the 75° advancing contact angle did not vary significantly with drop size. For the hydrophilic muscovite surface, the water drop wet the surface and an advancing contact angle of about 10° was found for the millidrops and submicron-drops. However, for the MD simulated nanodrops, attachment and spreading of the ~7 nm drop created a 2D film of molecular dimensions, the contact angle of which was difficult to define and varied from 0° to 17°. Perhaps of equal interest from the MD simulation results was that the spreading of the glycerol/water nanodrop at the muscovite surface resulted in crystallographic directional transport of water molecules to the extremities of the 2D film. Such separation and segregation left the center of the film with an increased concentration of glycerol. Based on these results, the line tension, which has been found in other investigations to account for contact angle decrease with a decrease in drop size, does not seem to be a significant factor in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of the adhesion-force lever-arm “a” on the Rock ‘n’ Roll resuspension model and how to compute it from contact mechanics

The paper proposes a methodology to fill a gap in the context of mechanistic particle resuspension models related to the adhesion and lift force lever arms ( a ): to date, only one experimental observation exists from a centrifuge experiment with a specific particle/surface pair which found r P / a = 100 and assumed that the contact points were symmetric with respect to the particle center. However, the Reeks and Hall’s (2001) model is highly sensitive to this parameter, which therefore cannot be used as-is for different particle diameters or materials. This paper proposes a methodology to compute the adhesion and lift force lever arms ( a A and a L , respectively) based on Atomic Force Microcopy (AFM) surface roughness measurements and contact mechanics arguments. In practice, a spherical, perfectly smooth particle is brought in contact (computationally) with the measured surface roughness and is then rotated by the point of contact to determine the two or more asperities over which the particle would sit on the surface. A method to compute the asperity radius of curvature is devised to compute the asperity deformation and the correct partitioning of the total deformation between the particle and the asperity is presented. For the glass surface under consideration, the asperity deformation was negligible, i.e., it was below the van der Waals radius, which is the limit of applicability of contact mechanics. The Reeks and Hall’s (2001) model is then extended to account for the joint probability of a A and a L . Significant differences in particle resuspended after a day in common atmospheric conditions are found between the approach that uses the lever-arm distributions or their mean values. Also, important differences are found when comparing the lever-arm distribution and r P / a = 100. Hence, one should be cautious of using r P / a = 100 for surface/particle pairs differing from those in the original study. Finally, limits of applicability of the theories used are presented together with considerations regarding how to extend the method to non-spherical particles and different materials.

42 ENGINEERING↗