Formation energies of low-indexed surfaces of tin dioxide terminated by nonmetals

The surface formation energies of four low-indexed surfaces, including (001), (100), (110) and (011), of tin dioxide (SnO2) terminated by nonmetals (H, N, O, F, Cl, Br, and I) have been studied with the frameworks of density functional theory. A strong dependence of relative surface stabilities on surface atoms has been presented based on the calculations. Several instructions, in particular the selection of specific precursors and morphology controlling agents, have been further illustrated as a guideline for experimentalists.

First-principle studies of the formation and diffusion of hydrogen vacancies in magnesium hydride

Ab initio density functional theory (DFT) calculations are performed to study the formation and diffusion of hydrogen vacancies on MgH2(110) surface and in bulk. We find that the formation energies for a single H-vacancy increase slightly from the surface to deep layers. The energies for creating adjacent surface divancacies at two inplane sites and at an inplane and a bridge site are even smaller than that for the formation of a single H-vacancy, a fact that is attributed to the strong vacancy−vacancy interactions. The diffusion of an H-vacancy from an in-plane site to a bridge site on the surface has the smallest activation barrier calculated at 0.15 eV and should be fast at room temperature. The activation barriers computed for H-vacancy diffusion from the surface into sublayers are all less than 0.70 eV, which is much smaller than the activation energy for desorption of hydrogen on the MgH2(110) surface (1.78−2.80 eV/H2). This suggests that surface desorption is more likely than vacancy diffusion to be rate determining, such that finding effective catalyst on the MgH2 surface to facilitate desorption will be very important for improving overall dehydrogenation performance.

Determining process model precision and generalization with weighted artificial negative events

Process mining encompasses the research area which is concerned with knowledge discovery from event logs. One common process mining task focuses on conformance checking, comparing discovered or designed process models with actual real-life behavior as captured in event logs in order to assess the “goodness” of the process model. This paper introduces a novel conformance checking method to measure how well a process model performs in terms of precision and generalization with respect to the actual executions of a process as recorded in an event log. Our approach differs from related work in the sense that we apply the concept of so-called weighted artificial negative events towards conformance checking, leading to more robust results, especially when dealing with less complete event logs that only contain a subset of all possible process execution behavior. In addition, our technique offers a novel way to estimate a process model’s ability to generalize. Existing literature has focused mainly on the fitness (recall) and precision (appropriateness) of process models, whereas generalization has been much more difficult to estimate. The described algorithms are implemented in a number of ProM plugins, and a Petri net conformance checking tool was developed to inspect process model conformance in a visual manner.

The use of artificial neural networks for identifying sustainable biodiesel feedstocks

Over the past few decades, biodiesel produced from oilseed crops and animal fat is receiving much attention as a renewable and sustainable alternative for automobile engine fuels, and particularly petroleum diesel. However, current biodiesel production is heavily dependent on edible oil feedstocks which are unlikely to be sustainable in the longer term due to the rising food prices and the concerns about automobile engine durability. Therefore, there is an urgent need for researchers to identify and develop sustainable biodiesel feedstocks which overcome the disadvantages of current ones. On the other hand, artificial neural network (ANN) modeling has been successfully used in recent years to gain new knowledge in various disciplines. The main goal of this article is to review recent literatures and assess the state of the art on the use of ANN as a modeling tool for future generation biodiesel feedstocks. Biodiesel feedstocks, production processes, chemical compositions, standards, physio-chemical properties and in-use performance are discussed. Limitations of current biodiesel feedstocks over future generation biodiesel feedstock have been identified. The application of ANN in modeling key biodiesel quality parameters and combustion performance in automobile engines is also discussed. This review has determined that ANN modeling has a high potential to contribute to the development of renewable energy systems by accelerating biodiesel research.

A bondgraph approach to formation control using relative state measurements

In this paper we apply port-Hamiltonian theory with the bondgraph modelling approach to the problem of formation control using partial measurements of relative positions. We present a control design that drives a group of vehicles to a desired formation without requiring inter-vehicle communications or global position and velocity measurements to be available. Our generic approach is applicable to any form of relative measurement between vehicles, but we specifically consider the important cases of relative bearings and relative distances. In the case of bearings, our theory closely relates to the field of image-based visual servo (IBVS) control. We present simulation results to support the developed theory.

Formation of polypyrrole and polythiophene within Cu2+- and H+-mordenite hosts studied by EPR and UV-VIS spectroscopy

The reactions of pyrrole and thiophene monomers in copper-exchanged mordenite have been investigated using EPR and UV–VIS absorption spectroscopy. The EPR spectra show a decrease in the intensity of the Cu2+ signal and the appearance of a radical signal due to the formation of oxidatively coupled oligomeric and/or polymeric species in the zeolite host. The reaction ceases when ca. 50% of the copper has reacted and differences in the form of the residual Cu2+ signal between the thiophene and pyrrole reactions suggest a greater degree of penetration of the reaction into the zeolite host for pyrrole, in agreement with previous XPS measurements. The EPR signal intensities show that the average length of the polymer chain that is associated with each radical centre is 15–20 and 5–7 monomer units for polypyrrole and polythiophene, respectively. The widths of the EPR signals suggest that these are at least partly due to small oligomers. The UV–VIS absorption spectra of the thiophene system show bands in three main regions: 2.8–3.0 eV (A), 2.3 eV (B) and 1.6–1.9 eV (D, E, F). Bands A and D–F occur in regions which have previously been observed for small oligomers, 4–6 monomer units in length. Band B is assigned to longer chain polythiophene molecules. We therefore conclude that the reaction between thiophene and copper-loaded mordenite produces a mixture of short oligomers together with some long chain polythiophene. The UV–VIS spectra of the pyrrole system show bands in the regions 3.6 eV (A), 2.7–3.0 eV (B, C) and 1.5–1.9 eV (D, F). Assignments of these bands are less certain than for the thiophene case because of the lack of literature data on the spectra of pyrrole oligomers.

Cross-linked poly(trimethylene carbonate-co-L-lactide) as a biodegradable, elastomeric scaffold for vascular engineering applications

A series of copolymers of trimethylene carbonate (TMC) and l-lactide (LLA) were synthesized and evaluated as scaffolds for the production of artificial blood vessels. The polymers were end-functionalized with acrylate, cast into films, and cross-linked using UV light. The mechanical, degradation, and biocompatibility properties were evaluated. High TMC polymers showed mechanical properties comparable to human arteries (Young’s moduli of 1.2–1.8 MPa and high elasticity with repeated cycling at 10% strain). Over 84 days degradation in PBS, the modulus and material strength decreased gradually. The polymers were nontoxic and showed good cell adhesion and proliferation over 7 days using human mesenchymal stem cells. When implanted into the rat peritoneal cavity, the polymers elicited formation of tissue capsules composed of myofibroblasts, resembling immature vascular smooth muscle cells. Thus, these polymers showed properties which were tunable and favorable for vascular tissue engineering, specifically, the growth of artificial blood vessels in vivo.

Mathematical modelling of soft callus formation in early murine bone repair

Fracture healing is a complicated coupling of many processes. Yet despite the apparent complexity, fracture repair is usually effective. There is, however, no comprehensive mathematical model addressing the multiple interactions of cells, cytokines and oxygen that includes extra-cellular matrix production and that results in the formation of the early stage soft callus. This thesis develops a one dimensional continuum transport model in the context of early fracture healing. Although fracture healing is a complex interplay of many local factors, critical components are identified and used to construct an hypothesis about regulation of the evolution of early callus formation. Multiple cell lines, cellular differentiation, oxygen levels and cytokine concentrations are examined as factors affecting this model of early bone repair. The model presumes diffusive and chemotactic cell migration mechanisms. It is proposed that the initial signalling regime and oxygen availability arising as consequences of bone fracture, are sufficient to determine the quantity and quality of early soft callus formation. Readily available software and purpose written algorithms have been used to obtain numerical solutions representative of various initial conditions. These numerical distributions of cellular populations reflect available histology obtained from murine osteotomies. The behaviour of the numerical system in response to differing initial conditions can be described by alternative in vivo healing pathways. An experimental basis, as illustrated in murine fracture histology, has been utilised to validate the mathematical model outcomes. The model developed in this thesis has potential for future extension, to incorporate processes leading to woven bone deposition, while maintaining the characteristics that regulate early callus formation.

Anatomic fitting of total artificial hearts for in vivo evaluation

Successful anatomic fitting of a total artificial heart (TAH) is vital to achieve optimal pump hemodynamics after device implantation. Although many anatomic fitting studies have been completed in humans prior to clinical trials, few reports exist that detail the experience in animals for in vivo device evaluation. Optimal hemodynamics are crucial throughout the in vivo phase to direct design iterations and ultimately validate device performance prior to pivotal human trials. In vivo evaluation in a sheep model allows a realistically sized representation of a smaller patient, for which smaller third-generation TAHs have the potential to treat. Our study aimed to assess the anatomic fit of a single device rotary TAH in sheep prior to animal trials and to use the data to develop a threedimensional, computer-aided design (CAD)-operated anatomic fitting tool for future TAH development. Following excision of the native ventricles above the atrio-ventricular groove, a prototype TAH was inserted within the chest cavity of six sheep (28–40 kg).Adjustable rods representing inlet and outlet conduits were oriented toward the center of each atrial chamber and the great vessels, with conduit lengths and angles recorded for future analysis. A threedimensional, CAD-operated anatomic fitting tool was then developed, based on the results of this study, and used to determine the inflow and outflow conduit orientation of the TAH. The mean diameters of the sheep left atrium, right atrium, aorta, and pulmonary artery were 39, 33, 12, and 11 mm, respectively. The center-to-center distance and outer-edge-to-outer-edge distance between the atria, found to be 39 ± 9 mm and 72 ± 17 mm in this study, were identified as the most critical geometries for successful TAH connection. This geometric constraint restricts the maximum separation allowable between left and right inlet ports of a TAH to ensure successful alignment within the available atrial circumference.

Evaluation of inflow cannulation site for implantation of right-sided rotary ventricular assist device

Right heart dysfunction is one of the most serious complications following implantation of a left ventricular assist device (LVAD), often leading to the requirement for short or long term right ventricular support (RVAD). The inflow cannulation site induces major haemodynamic changes and so there is a need to optimize the site used depending on the patient's condition. Therefore, this study evaluated and compared the haemodynamic influence of right atrial (RAC) and right ventricular (RVC) inflow cannulation sites. An in-vitro, variable heart failure, mock circulation loop was used to compare RAC and RVC in mild and severe biventricular heart failure (BHF) conditions. In the severe BHF condition, higher ventricular ejection fraction (RAC: 13.6%, RVC: 32.7%) and thus improved heart chamber and RVAD washout was observed with RVC, which suggested this strategy might be preferable for long term support (ie. bridge to transplant or destination therapy) to reduce the risk of thrombus formation. In the mild BHF condition, higher pulmonary valve flow (RAC: 3.33 L/min, RVC: 1.97 L/min) and lower right ventricular stroke work (RAC: 0.10 W, RVC: 0.13 W) and volumes were recorded with RAC. These results indicate an improved potential for myocardial recovery, thus RAC should be chosen in this condition. This in-vitro study suggests that RVAD inflow cannulation site should be chosen on a patient-specific basis with a view to the support strategy to promote myocardial recovery or reduce the risk of long-term complications.

Mussel-inspired bioceramics with self-assembled Ca-P/polydopamine composite nanolayer : preparation, formation mechanism, improved cellular bioactivity and osteogenic differentiation of bone marrow stromal cells

The nanostructured surface of biomaterials plays an important role in improving their in vitro cellular bioactivity as well as stimulating in vivo tissue regeneration. Inspired by the mussel’s adhesive versatility, which is thought to be due to the plaque–substrate interface being rich in 3,4-dihydroxy-L-phenylalamine (DOPA) and lysine amino acids, in this study we developed a self-assembly method to prepare a uniform calcium phosphate (Ca-P)/polydopamine composite nanolayer on the surface of b-tricalcium phosphate (b-TCP) bioceramics by soaking b-TCP bioceramics in Tris–dopamine solution. It was found that the addition of dopamine, reaction temperature and reaction time are three key factors inducing the formation of a uniform Ca-P/polydopamine composite nanolayer. The formation mechanism of a Ca-P/polydopamine composite nanolayer involved two important steps: (i) the addition of dopamine to Tris–HCl solution decreases the pH value and accelerates Ca and P ionic dissolution from the crystal boundaries of b-TCP ceramics; (ii) dopamine is polymerized to form self-assembled polydopamine film and, at the same time, nanosized Ca-P particles are mineralized with the assistance of polydopamine, in which the formation of polydopamine occurs simultaneously with Ca-P mineralization (formation of nanosized microparticles composed of calcium phosphate-based materials), and finally a self-assembled Ca-P/polydopamine composite nanolayer forms on the surface of the b-TCP ceramics. Furthermore, the formed self-assembled Ca-P/polydopamine composite nanolayer significantly enhances the surface roughness and hydrophilicity of b-TCP ceramics, and stimulates the attachment, proliferation, alkaline phosphate (ALP) activity and bone-related gene expression (ALP, OCN, COL1 and Runx2) of human bone marrow stromal cells. Our results suggest that the preparation of self-assembled Ca-P/polydopamine composite nanolayers is a viable method to modify the surface of biomaterials by significantly improving their surface physicochemical properties and cellular bioactivity for bone regeneration application.

Microstructure of an artificial grain boundary weak link in an YBa2Cu3O(7-δ) thin film grown on a (100)(110), [001]-tilt Y-ZrO2 bicrystal

The microstructure of an artificial grain boundary in an YBa2Cu3O7-δ (YBCO) thin film grown on a (100)(110), [001]-tilt yttria-stabilized-zirconia (YSZ) bicrystal substrate has been studied using transmission electron microscopy (TEM). The orientation relationship between the YBCO film and the YSZ substrate was [001]YBCO∥[001]YSZ and [110]YBCO∥[100]YSZ for each half of the bicrystal film. However, the exact boundary geometry of the bicrystal substrate was not transferred to the film. The substrate boundary was straight while the film boundary was wavy. In several cases there was bending of the lattice confined within a distance of a few basal-plane lattice spacings from the boundary plane and microfaceting. No intergranular secondary phase was observed but about 25% of the boundary was covered by c-axis-tilted YBCO grains and a-axis-oriented grains, both of which were typically adjacent to CuO grains or surrounded by a thin Cu-rich amorphous layer.

Microstructure and properties of artificial grain boundaries in epitaxial YBA2Cu3O7-δ thin films grown on [001] tilt YZrO2 bicrystals

The microstructure of artificial grain boundaries in YBa2Cu3O7-δ (YBCO) thin films grown on [001] tilt YZrO2 (YSZ) bicrystal substrates has been characterized using transmission electron microscopy and atomic force microscopy. Despite a relatively straight morphology of the substrate boundaries, the film boundaries were wavy. The waviness was a result of the combined effects of grooving at the substrate boundaries prior to the film deposition and an island-growth mechanism for YBCO on YSZ substrates. The dihedral angle of the groove walls varied with the misorientation angle and depended on the symmetry of the substrate boundary. The amplitudes of the film boundary waviness compared well with the widths of the grooves. In addition, the grooves induced local bending of the YBCO lattice planes and additional tilt components perpendicular to the c-axis close to the film boundaries. © 1995.

Properties of artificial grain boundary weak links grown on Y-ZrO 2 bicrystals

Weak links were fabricated by pulsed laser deposition of YBa 2Cu3Ox thin films on Y-ZrO2 bicrystal substrates. They were formed by transferring the bicrystal boundary into the epitaxial film during the film growth. Their properties were determined by the misorientation angle ( theta ) between the two halves of the bicrystal. The transport properties of the weak links were studied as a function of theta and an exponential dependence of the weak link critical current density was observed for angles up to 45 degrees . Clear Josephson effects with good microwave and magnetic field response were observed.

Weak links and dc SQUIDS on artificial nonsymmetric grain boundaries in YBa2Cu3O7-δ

We have studied weak links and dc-SQUIDs made from pulsed laser deposited YBa2Cu3O7-δ thin films on Y-ZrO 2 bicrystal substrates. The transport properties of the weak links were studied as a function of the misorientation angle (θ) between the two halves of the bicrystal and an exponential dependence of the weak link critical current density was observed for angles up to 40°at 77 K. Josephson effects with clear microwave and magnetic field responses were observed. An optimum dc-SQUID performance at 77 K was obtained for θ=32°. At this temperature, we achieved a periodic magnetic field response with a modulation depth of 12 μV.