Principles governing control of aggregation and dispersion of aqueous graphene oxide

Controlling the structure of graphene oxide (GO) phases and their smaller analogues, graphene (oxide) quantum dots (GOQDs), is vitally important for any of their widespread intended applications: highly ordered arrangements of nanoparticles for thin-film or membrane applications of GO, dispersed nanoparticles for composite materials and three-dimensional porous arrangements for hydrogels. In aqueous environments, it is not only the chemical composition of the GO flakes that determines their morphologies; external factors such as pH and the coexisting cations also influence the structures formed. By using accurate models of GO that capture the heterogeneity of surface oxidation and very large-scale coarse-grained molecular dynamics that can simulate the behaviour of GO at realistic sizes of GOQDs, the driving forces that lead to the various morphologies in aqueous solution are resolved. We find the morphologies are determined by a complex interplay between electrostatic, [Formula: see text]-[Formula: see text] and hydrogen bonding interactions. Assembled morphologies can be controlled by changing the degree of oxidation and the pH. In acidic aqueous solution, the GO flakes vary from fully aggregated over graphitic domains to partial aggregation via hydrogen bonding between hydroxylated domains, leading to the formation of planar extended flakes at high oxidation ratios and stacks at low oxidation ratios. At high pH, where the edge carboxylic acid groups are deprotonated, electrostatic repulsion leads to more dispersion, but a variety of aggregation behaviour is surprisingly still observed: over graphitic regions, via hydrogen bonding and "face-edge" interactions. Calcium ions cause additional aggregation, with a greater number of "face-face" and "edge-edge" aggregation mechanisms, leading to irregular aggregated structures. "Face-face" aggregation mechanisms are enhanced by the GO flakes possessing distinct domains of hydroxylated and graphitic regions, with [Formula: see text]-[Formula: see text] and hydrogen bonding interactions prevalent between these regions on aggregated flakes respectively. These findings furnish explanations for the aggregation characteristics of GO and GOQDs, and provide computational methods to design directed synthesis routes for self-assembled and associated applications

Mechanism of Exfoliation and Prediction of Materials Properties of Clay-Polymer Nanocomposites from Multiscale Modeling

We describe the mechanism that leads to full exfoliation and dispersion of organophilic clays when mixed with molten hydrophilic polymers. This process is of fundamental importance for the production of clay-polymer nanocomposites with enhanced materials properties. The chemically specific nature of our multiscale approach allows us to probe how chemistry, in combination with processing conditions, produces such materials properties at the mesoscale and beyond. In general agreement with experimental observations, we find that a higher grafting density of charged quaternary ammonium surfactant ions promotes exfoliation, by a mechanism whereby the clay sheets slide transversally over one another. We can determine the elastic properties of these nanocomposites; exfoliated and partially exfoliated morphologies lead to substantial enhancement of the Young's modulus, as found experimentally

Principles Governing Control of Aggregation and Dispersion of Graphene and Graphene Oxide in Polymer Melts

Controlling the structure of graphene and graphene oxide (GO) phases is vitally important for any of its widespread intended applications: highly ordered arrangements of nanoparticles are needed for thin‐film or membrane applications of GO, dispersed nanoparticles for composite materials, and 3D porous arrangements for hydrogels. By combining coarse‐grained molecular dynamics and newly developed accurate models of GO, the driving forces that lead to the various morphologies are resolved. Two hydrophilic polymers, poly(ethylene glycol) (PEG) and poly(vinyl alcohol) (PVA), are used to illustrate the thermodynamically stable morphologies of GO and relevant dispersion mechanisms. GO self‐assembly can be controlled by changing the degree of oxidation, varying from fully aggregated over graphitic domains to intercalated assemblies with polymer bilayers between sheets. The long‐term stability of a dispersion is extremely important for many commercial applications of GO composites. For any degree of oxidation, GO does not disperse in PVA as a thermodynamic equilibrium product, whereas in PEG dispersions are only thermodynamically stable for highly oxidized GO. These findings—validated against the extensive literature on GO systems in organic solvents—furnish quantitative explanations for the empirically unpredictable aggregation characteristics of GO and provide computational methods to design directed synthesis routes for diverse self‐assemblies and applications

Toward High Fidelity Materials Property Prediction from Multiscale Modeling and Simulation

The current approach to materials discovery and design remains dominated by experimental testing, frequently based on little more than trial and error. With the advent of ever more powerful computers, rapid, reliable, and reproducible computer simulations are beginning to represent a feasible alternative. As high performance computing reaches the exascale, exploiting the resources efficiently presents interesting challenges and opportunities. Multiscale modeling and simulation of materials are extremely promising candidates for exploiting these resources based on the assumption of a separation of scales in the architectures of nanomaterials. Examples of hierarchical and concurrent multiscale approaches are presented which benefit from the weak scaling of monolithic applications, thereby efficiently exploiting large scale computational resources. Several multiscale techniques, incorporating the electronic to the continuum scale, which can be applied to the efficient design of a range of nanocomposites, are discussed. Then the work on the development of a software toolkit designed to provide verification, validation, and uncertainty quantification to support actionable prediction from such calculations is discussed

Micromechanical exfoliation of graphene on the atomistic scale

Mechanical exfoliation techniques are widely used to create high quality graphene samples for analytical use. Increasingly, mechanical methods are used to create large quantities of graphene, yet there is surprisingly little molecular insight into the mechanisms involved. We study the exfoliation of graphene with sticky tape using molecular dynamics. This is made possible by using a recently developed molecular dynamics forcefield, GraFF, to represent graphene's dispersion interactions. For nano-sized flakes we observe two different mechanisms depending on the polymer-adhesive used. A peeling mechanism which mixes shearing and normal mode exfoliation promotes synthesis of graphene rather than many-layered graphite. Armed with this new chemical insight we discuss the experimental methods that could preferentially produce graphene by mechanical exfoliation. We also introduce a mathematical model describing the repeated exfoliation of graphite

A Review of Drive Cycles for Electrochemical Propulsion

Automotive drive cycles have existed since the 1960s. They started as requirements as being solely used for emissions testing. During the past decade, they became popular with scientists and researchers in the testing of electrochemical vehicles and power devices. They help simulate realistic driving scenarios anywhere from system to component-level design. This paper aims to discuss the complete history of these drive cycles and their validity when used in an electrochemical propulsion scenario, namely with the use of proton exchange membrane fuel cells (PEMFC) and lithium-ion batteries. The differences between two categories of drive cycles, modal and transient, were compared; and further discussion was provided on why electrochemical vehicles need to be designed and engineered with transient drive cycles instead of modal. Road-going passenger vehicles are the main focus of this piece. Similarities and differences between aviation and marine drive cycles are briefly mentioned and compared and contrasted with road cycles. The construction of drive cycles and how they can be transformed into a ‘power cycle’ for electrochemical device sizing purposes for electrochemical vehicles are outlined; in addition, how one can use power cycles to size electrochemical vehicles of various vehicle architectures are suggested, with detailed explanations and comparisons of these architectures. A concern with using conventional drive cycles for electrochemical vehicles is that these types of vehicles behave differently compared to combustion-powered vehicles, due to the use of electrical motors rather than internal combustion engines, causing different vehicle behaviours and dynamics. The challenges, concerns, and validity of utilising ‘general use’ drive cycles for electrochemical purposes are discussed and critiqued

The Role of Graphene in Enhancing the Material Properties of Thermosetting Polymers

Graphene continues to attract considerable attention from the materials science community through its potential for improving the mechanical properties of polymer thermosets, yet there remains considerable uncertainty over the underlying mechanisms. The effect of introducing graphene sheets to a typical thermosetting polymer network on mechanical behaviour is explored here through concurrently coupling molecular dynamics with a finite element solver. In this multiscale approach, Graphene is observed to act in two ways: as passive microscopic defects, dispersing crack propagation (high deformation); and as active geometric constraints, impeding polymer conformational changes (low deformation). By contrast, single‐scale atomistic simulations alone predict little measurable difference in the properties of the graphene‐enhanced epoxy resins as compared with the pure polymer case. The multiscale model predicts that epoxy resins reinforced with graphene nanoparticles exhibit enhanced overall elastoplastic properties, reducing strain energy dissipation by up to 70%. Importantly, this is only observed when taking into account the complex boundary conditions, mainly involving shear, arising from coupling physics on length scales separated by five orders of magnitude. The approach herein clearly highlights a novel role of graphene nanoparticles in actively constraining the surrounding polymer matrix, impeding local dissipative mechanisms, and resisting shear deformation

Platinum deposition on functionalised graphene for corrosion resistant oxygen reduction electrodes

Graphene-related materials are promising supports for electrocatalysts due to their stability and high surface area. Their innate surface chemistries can be controlled and tuned via functionalisation to improve the stability of both the carbon support and the metal catalyst. Functionalised graphenes were prepared using either aryl diazonium functionalisation or non-destructive chemical reduction, to provide groups adapted for platinum deposition. XPS and TGA-MS measurements confirmed the presence of polyethyleneglycol and sulfur-containing functional groups, and provided consistent values for the extent of the reactions. The deposited platinum nanoparticles obtained were consistently around 2 nm via reductive chemistry and around 4 nm via the diazonium route. Although these graphene-supported electrocatalysts provided a lower electrochemical surface area (ECSA), functionalised samples showed enhanced specific activity compared to a commercial platinum/carbon black system. Accelerated stress testing (AST) showed improved durability for the functionalised graphenes compared to the non-functionalised materials, attributed to edge passivation and catalyst particle anchoring

The predictive role of serum and bronchoalveolar lavage cytokines and adhesion molecules for acute respiratory distress syndrome development and outcome

BACKGROUND: The predictive role of many cytokines and adhesion molecules has not been studied systematically in acute respiratory distress syndrome (ARDS). METHODS: We measured prospectively tumour necrosis factor alpha (TNF-α), interleukin (IL)-1, soluble vascular adhesion molecule-1 (VCAM-1) and soluble intercellular adhesion molecule-1 (ICAM-1) in serum and bronchoalveolar lavage fluid (BALF) within 2 hours following admission, in 65 patients. The patients were divided into: those fulfilling the criteria for ARDS (n = 23, group A), those who were pre-ARDS and who developed ARDS within 24 hours (n = 14, group B), and those on pre-ARDS but who never developed ARDS (n = 28, group C). RESULTS: All the measured molecules were only found at higher levels in the serum of patients that died either with or without ARDS (P < 0.05 – P < 0.0001). Patients at risk exhibited a good negative predictive value (NPV) of the measured molecules for ARDS development both in their serum (89 to 95%) and BALF (86 to 92%) levels. In contrast to BALF, serum levels of IL-1 and adhesion molecules exhibited a good NPV (68 to 96%), sensitivity (60 to 88%) and survival specificity (74 to 96%) in all groups. All molecules in serum and BALF IL-1 were correlated with the APACHE II (P < 0.05 – P < 0.0001). Serum and BALF IL-1 as well as BALF TNF-α were negatively correlated to PaO(2)/FiO(2) (all P < 0.05). CONCLUSIONS: The studied molecules have good NPV for ARDS development both in serum and BALF. Serum rather than BALF levels seem to be related to outcome

How are "teaching the teachers" courses in evidence based medicine evaluated? A systematic review

Background Teaching of evidence-based medicine (EBM) has become widespread in medical education. Teaching the teachers (TTT) courses address the increased teaching demand and the need to improve effectiveness of EBM teaching. We conducted a systematic review of assessment tools for EBM TTT courses. To summarise and appraise existing assessment methods for teaching the teachers courses in EBM by a systematic review. Methods We searched PubMed, BioMed, EmBase, Cochrane and Eric databases without language restrictions and included articles that assessed its participants. Study selection and data extraction were conducted independently by two reviewers. Results Of 1230 potentially relevant studies, five papers met the selection criteria. There were no specific assessment tools for evaluating effectiveness of EBM TTT courses. Some of the material available might be useful in initiating the development of such an assessment tool. Conclusion There is a need for the development of educationally sound assessment tools for teaching the teachers courses in EBM, without which it would be impossible to ascertain if such courses have the desired effect