Controlling magnetoelectric coupling by nanoscale phase transformation in strain engineered bismuth ferrite

The magnetoelectric coupling in multiferroic materials is promising for a wide range of applications, yet manipulating magnetic ordering by electric field proves elusive to obtain and difficult to control. In this paper, we explore the prospect of controlling magnetic ordering in misfit strained bismuth ferrite (BiFeO3, BFO) films, combining theoretical analysis, numerical simulations, and experimental characterizations. Electric field induced transformation from a tetragonal phase to a distorted rhombohedral one in strain engineered BFO films has been identified by thermodynamic analysis, and realized by scanning probe microscopy (SPM) experiment. By breaking the rotational symmetry of a tip-induced electric field as suggested by phase field simulation, the morphology of distorted rhombohedral variants has been delicately controlled and regulated. Such capabilities enable nanoscale control of magnetoelectric coupling in strain engineered BFO films that is difficult to achieve otherwise, as demonstrated by phase field simulations.

Toward Quantitative Electrochemical Measurements on the Nanoscale by Scanning Probe Microscopy: Environmental and Current Spreading Effects

The application of electric bias across tip–surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes, remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. We find that reaction processes are highly dependent on the nature of the counter electrode and environmental conditions. Using a nondepleting Li counter electrode, Li particles could grow significantly larger and faster than a depleting counter electrode. Significant Li ion depletion leads to the inability for further Li reduction. Time studies suggest that Li diffusion replenishes the vacant sites after 12 h. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

Influence of test methodology and probe geometry on nanoscale fatigue mechanisms of diamond-like carbon thin film

The aim of this paper is to investigate the mechanism of nanoscale fatigue using nano-impact and multiple-loading cycle nanoindentation tests, and compare it to previously reported findings of nanoscale fatigue using integrated stiffness and depth sensing approach. Two different film loading mechanism, loading history and indenter shapes are compared to comprehend the influence of test methodology on the nanoscale fatigue failure mechanisms of DLC film. An amorphous 100 nm thick DLC film was deposited on a 500 μm silicon substrate using sputtering of graphite target in pure argon atmosphere. Nano-impact and multiple-load cycle indentations were performed in the load range of 100 μN to 1000 μN and 0.1 mN to 100 mN, respectively. Both test types were conducted using conical and Berkovich indenters. Results indicate that for the case of conical indenter, the combination of nano-impact and multiple-loading cycle nanoindentation tests provide information on the life and failure mechanism of DLC film, which is comparable to the previously reported findings using the integrated stiffness and depth sensing approach. However, the comparison of results is sensitive to the applied load, loading mechanism, test-type and probe geometry. The loading mechanism and load history is therefore critical which also leads to two different definitions of film failure. The choice of exact test methodology, load and probe geometry should therefore be dictated by the in-service tribological conditions, and where necessary both test methodologies can be used to provide better insights of failure mechanism. Molecular dynamics (MD) simulations of the elastic response of nanoindentation is reported, which indicates that the elastic modulus of the film measured using MD simulation was higher than that experimentally measured. This difference is attributed to the factors related to the presence of material defects, crystal structure, residual stress, indenter geometry and loading/unloading rate differences between the MD and experimental results.

Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

Density functional theory study of mixed-phase TiO2: heterostructures and electronic properties

In this work, density functional theory calculations have been performed to study the geometric, electronic, and energetic properties of two-phase TiO2 composites built by joining two single-phase TiO2 slabs, aiming at verifying possible improvement of the photo-activities of the composites through phase separation of excitons. We find that such desired electronic properties can be determined by several factors. When both the HOMO and LUMO levels of one of the two single-phase TiO2 slabs are higher than the corresponding ones of the other, the composite may have native electronic structures with phase-separated HOMO-LUMO states, especially when the two slabs exhibit highly matched surface lattices. For those pairs of TiO2 slabs with the HOMO and LUMO levels of one phase being within the range of those of the other, though the energetically favored composite give HOMO-LUMO states within one phase, one may still be able to separate them and move the HOMO state to the interface region by destabilizing the interactions between the two slabs.

Identifying the trend of reactivity for sp2 materials: an electron delocalization model from first principles calculations

The reactivity of sp² carbon materials is studied using the adsorption and dissociation of O₂ on graphene and graphene oxide as model systems. The reactions on the basal plane, zigzag and armchair edges of graphene and graphene oxide with different oxygen-containing groups are calculated using first principles calculations. Two Brønsted-Evans- Polanyi relationships are identified and an electron delocalization model is suggested to understand the general trend of reactivity for sp² carbon materials.

Selection and characterisation of geological materials for use as geopolymer precursors

Geopolymer binders are generally formed by reacting powdered aluminosilicate precursors with alkali silicate activators. Most research to date has concentrated on using either pulverised fuel ash or high purity dehydroxylated kaolin (metakaolin) in association with ground granulated blast furnace slag as the main precursor material. However, recently, attention has turned to alternative calcined clays that are abundant throughout the globe and have lower kaolinite contents than commercially available metakaolins. Due to the lack of clear and simple screening protocols enabling assessment of such geological resources for use as precursors in geopolymer systems, the present paper presents results from experimental work that was carried out to develop a functional binder using materials containing kaolinite taken from the Interbasaltic Formation of Northern Ireland. The influence of mineralogy has been examined, and a screening process, using three Interbasaltic materials as examples, that will assist in the rapid selection of suitable geopolymeric precursors from such materials is outlined.

Metallosupramolecular Materials for Electronic Applications: Molecular Boolean Computation

It is an exciting era for molecular computation because molecular logic gates are being pushed in new directions. The use of sulfur rather than the commonplace nitrogen as the key receptor atom in metal ion sensors is one of these directions; plant cells coming within the jurisdiction of fluorescent molecular thermometers is another, combining photochromism with voltammetry for molecular electronics is yet another. Two-input logic gates benefit from old ideas such as rectifying bilayer electrodes, cyclodextrin-enhanced room-temperature phosphorescence, steric hindrance, the polymerase chain reaction, charge transfer absorption of donor–acceptor complexes and lectin–glycocluster interactions. Furthermore, the concept of photo-uncaging enables rational ways of concatenating logic gates. Computational concepts are also applied to potential cancer theranostics and to the selective monitoring of neurotransmitters in situ. Higher numbers of inputs are also accommodated with the concept of functional integration of gates, where complex input–output patterns are sought out and analysed. Molecular emulation of computational components such as demultiplexers and parity generators/checkers are achieved in related ways. Complexity of another order is tackled with molecular edge detection routines.

Molecular dynamics simulation (MDS) to study nanoscale machining processes

Molecular Dynamics Simulations (MDS) are constantly being used to make important contributions to our fundamental understanding of material behaviour, at the atomic scale, for a variety of thermodynamic processes. This chapter shows that molecular dynamics simulation is a robust numerical analysis tool in addressing a range of complex nanofinishing (machining) problems that are otherwise difficult or impossible to understand using other methods. For example the mechanism of nanometric cutting of silicon carbide is influenced by a number of variables such as machine tool performance, machining conditions, material properties, and cutting tool performance (material microstructure and physical geometry of the contact) and all these variables cannot be monitored online through experimental examination. However, these could suitably be studied using an advanced simulation based approach such as MDS. This chapter details how MD simulation can be used as a research and commercial tool to understand key issues of ultra precision manufacturing research problems and a specific case was addressed by studying diamond machining of silicon carbide. While this is appreciable, there are a lot of challenges and opportunities in this fertile area. For example, the world of MD simulations is dependent on present day computers and the accuracy and reliability of potential energy functions [109]. This presents a limitation: Real-world scale simulation models are yet to be developed. The simulated length and timescales are far shorter than the experimental ones which couples further with the fact that contact loading simulations are typically done in the speed range of a few hundreds of m/sec against the experimental speed of typically about 1 m/sec [17]. Consequently, MD simulations suffer from the spurious effects of high cutting speeds and the accuracy of the simulation results has yet to be fully explored. The development of user-friendly software could help facilitate molecular dynamics as an integral part of computer-aided design and manufacturing to tackle a range of machining problems from all perspectives, including materials science (phase of the material formed due to the sub-surface deformation layer), electronics and optics (properties of the finished machined surface due to the metallurgical transformation in comparison to the bulk material), and mechanical engineering (extent of residual stresses in the machined component) [110]. Overall, this chapter provided key information concerning diamond machining of SiC which is classed as hard, brittle material. From the analysis presented in the earlier sections, MD simulation has helped in understanding the effects of crystal anisotropy in nanometric cutting of 3C-SiC by revealing the atomic-level deformation mechanisms for different crystal orientations and cutting directions. In addition to this, the MD simulation revealed that the material removal mechanism on the (111) surface of 3C-SiC (akin to diamond) is dominated by cleavage. These understandings led to the development of a new approach named the “surface defect machining” method which has the potential to be more effective to implement than ductile mode micro laser assisted machining or conventional nanometric cutting.

Nonconservative current-driven dynamics: beyond the nanoscale

Long metallic nanowires combine crucial factors for nonconservative current-driven atomic motion. These systems have degenerate vibrational frequencies, clustered about a Kohn anomaly in the dispersion relation, that can couple under current to form nonequilibrium modes of motion growing exponentially in time. Such motion is made possible by nonconservative current-induced forces on atoms, and we refer to it generically as the waterwheel effect. Here the connection between the waterwheel effect and the stimulated directional emission of phonons propagating along the electron flow is discussed in an intuitive manner. Nonadiabatic molecular dynamics show that waterwheel modes self-regulate by reducing the current and by populating modes in nearby frequency, leading to a dynamical steady state in which nonconservative forces are counter-balanced by the electronic friction. The waterwheel effect can be described by an appropriate effective nonequilibrium dynamical response matrix. We show that the current-induced parts of this matrix in metallic systems are long-ranged, especially at low bias. This nonlocality is essential for the characterisation of nonconservative atomic dynamics under current beyond the nanoscale.

Porous Materials with Tunable Structure and Mechanical Properties via Templated Layer-by-Layer Assembly

The deposition of stiff and strong coatings onto porous templates offers a novel strategy for fabricating macroscale materials with controlled architectures at the micro- and nanoscale. Here, layer-by-layer assembly is utilized to fabricate nanocomposite-coated foams with highly customizable properties by depositing polymer–nanoclay coatings onto open-cell foam templates. The compressive mechanical behavior of these materials evolves in a predictable manner that is qualitatively captured by scaling laws for the mechanical properties of cellular materials. The observed and predicted properties span a remarkable range of density-stiffness space, extending from regions of very soft elastomer foams to very stiff, lightweight honeycomb and lattice materials.

Intrinsically flexible electronic materials for smart device applications

A novel method to fabricate chemically linked conducting polymer–biopolymer composites that are intrinsically flexible and conducting for functional electrode applications is presented. Polypyrrole was synthesised in situ during the cellulose regeneration process using the 1-butyl-3-methylimidazolium chloride ionic liquid as a solvent medium. The obtained polypyrrole–cellulose composite was chemically blended and showed flexible polymer properties while retaining the electronic properties of a conducting polymer. Addition of an ionic liquid such as trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, enhanced the flexibility of the composite. The functional application of these materials in the electrochemically controlled release of a model drug has been demonstrated. This strategy opens up a new design for a wide spectrum of materials for smart electronic device applications wherein the functionality of doping and de-doping of conducting polymers is retained and their processability issue is addressed by exploiting an ionic liquid route.