The use of atomic force microscopy in investigating particle caking mechanisms

Spray-dried materials are being used increasingly in industries such as food, detergent and pharmaceutical manufacture. Spray-dried sodium carbonate is an important product that has a great propensity to cake; its moisture-sorption properties are very different to the crystalline and amorphous species, with a great affinity for atmospheric moisture. This work demonstrates how the noncontact surface analysis of individual particles using atomic force microscopy can highlight the possible mechanisms of unwanted agglomeration. The nondestructive nature of this method allows cycling of localised humidity in situ and repeated scanning of the same particle area. The resulting topography and phase scans showed that humidity cycling caused changes in the distribution of material phases that were not solely dependent on topographical changes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Developing a decision framework for the strategic sourcing of biomass

The deployment of bioenergy technologies is a key part of UK and European renewable energy policy. A key barrier to the deployment of bioenergy technologies is the management of biomass supply chains including the evaluation of suppliers and the contracting of biomass. In the undeveloped biomass for energy market buyers of biomass are faced with three major challenges during the development of new bioenergy projects. What characteristics will a certain supply of biomass have, how to evaluate biomass suppliers and which suppliers to contract with in order to provide a portfolio of suppliers that best satisfies the needs of the project and its stakeholder group whilst also satisfying crisp and non-crisp technological constraints. The problem description is taken from the situation faced by the industrial partner in this research, Express Energy Ltd. This research tackles these three areas separately then combines them to form a decision framework to assist biomass buyers with the strategic sourcing of biomass. The BioSS framework. The BioSS framework consists of three modes which mirror the development stages of bioenergy projects. BioSS.2 mode for early stage development, BioSS.3 mode for financial close stage and BioSS.Op for the operational phase of the project. BioSS is formed of a fuels library, a supplier evaluation module and an order allocation module, a Monte-Carlo analysis module is also included to evaluate the accuracy of the recommended portfolios. In each mode BioSS can recommend which suppliers should be contracted with and how much material should be purchased from each. The recommended blend should have chemical characteristics within the technological constraints of the conversion technology and also best satisfy the stakeholder group. The fuels library is made up from a wide variety of sources and contains around 100 unique descriptions of potential biomass sources that a developer may encounter. The library takes a wide data collection approach and has the aim of allowing for estimates to be made of biomass characteristics without expensive and time consuming testing. The supplier evaluation part of BioSS uses a QFD-AHP method to give importance weightings to 27 different evaluating criteria. The evaluating criteria have been compiled from interviews with stakeholders and policy and position documents and the weightings have been assigned using a mixture of workshops and expert interview. The weighted importance scores allow potential suppliers to better tailor their business offering and provides a robust framework for decision makers to better understand the requirements of the bioenergy project stakeholder groups. The order allocation part of BioSS uses a chance-constrained programming approach to assign orders of material between potential suppliers based on the chemical characteristics of those suppliers and the preference score of those suppliers. The optimisation program finds the portfolio of orders to allocate to suppliers to give the highest performance portfolio in the eyes of the stakeholder group whilst also complying with technological constraints. The technological constraints can be breached if the decision maker requires by setting the constraint as a chance-constraint. This allows a wider range of biomass sources to be procured and allows a greater overall performance to be realised than considering crisp constraints or using deterministic programming approaches. BioSS is demonstrated against two scenarios faced by UK bioenergy developers. The first is a large scale combustion power project, the second a small scale gasification project. The Bioss is applied in each mode for both scenarios and is shown to adapt the solution to the stakeholder group importance and the different constraints of the different conversion technologies whilst finding a globally optimal portfolio for stakeholder satisfaction.

Effect of thermal residual stresses on fatigue crack opening and propagation behavior in an Al/SiCp metal matrix composite

The effects of a thermal residual stress field on fatigue crack growth in a silicon carbide particle-reinforced aluminum alloy have been measured. Stress fields were introduced into plates of material by means of a quench from a solution heat-treatment temperature. Measurements using neutron diffraction have shown that this introduces an approximately parabolic stress field into the plates, varying from compressive at the surfaces to tensile in the center. Long fatigue cracks were grown in specimens cut from as-quenched plates and in specimens which were given a stress-relieving overaging heat treatment prior to testing. Crack closure levels for these cracks were determined as a function of the position of the crack tip in the residual stress field, and these are shown to differ between as-quenched and stress-relieved samples. By monitoring the compliance of the specimens during fatigue cycling, the degree to which the residual stresses close the crack has been evaluated. © 1995 The Minerals, Metals & Material Society.

Analysis of functional materials by X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy (XPS) can play an important role in guiding the design of new materials, tailored to meet increasingly stringent constraints on performance devices, by providing insight into their surface compositions and the fundamental interactions between the surfaces and the environment. This chapter outlines the principles and application of XPS as a versatile, chemically specific analytical tool in determining the electronic structures and (usually surface) compositions of constituent elements within diverse functional materials. Advances in detector electronics have opened the way for development of photoelectron microscopes and instruments with XPS imaging capabilities. Advances in surface science instrumentation to enable time-resolved spectroscopic measurements offer exciting opportunities to quantitatively investigate the composition, structure and dynamics of working catalyst surfaces. Attempts to study the effects of material processing in realistic environments currently involves the use of high- or ambient-pressure XPS in which samples can be exposed to reactive environments.

Application of Artificial Intelligence Methods to Computer Design of Inorganic Compounds

In this paper the main problems for computer design of materials, which would have predefined properties, with the use of artificial intelligence methods are presented. The DB on inorganic compound properties and the system of DBs on materials for electronics with completely assessed information: phase diagram DB of material systems with semiconducting phases and DB on acousto-optical, electro-optical, and nonlinear optical properties are considered. These DBs are a source of information for data analysis. Using the DBs and artificial intelligence methods we have predicted thousands of new compounds in ternary, quaternary and more complicated chemical systems and estimated some of their properties (crystal structure type, melting point, homogeneity region etc.). The comparison of our predictions with experimental data, obtained later, showed that the average reliability of predicted inorganic compounds exceeds 80%. The perspectives of computational material design with the use of artificial intelligence methods are considered.

Fracture and viscoelastic properties of asphalt binders during fatigue and rest periods

Viscoelastic asphalt binder plays an important role in bonding individual aggregate particles and contributes to the durability and stability of asphalt pavement. When asphalt binder is subjected to cyclic loading, deformation and fracture may develop simultaneously within it, leading to the deterioration of material properties and eventually fatigue failure. Research has found that some degree of recovery may develop if rest periods are applied after fatigue deterioration. However, it is not clear whether such recovery is caused by fracture healing, viscoelastic recovery, or both. This paper presents an analysis to differentiate the contributions of fracture healing and viscoelastic recovery to the asphalt binder during rest periods. It also evaluates the damage caused by deformation and fracture during a fatigue process. It is found that viscoelastic recovery plays an important role in the instant increase in the dynamic shear modulus at the beginning of the rest period. The effect of fracture healing on dynamic shear modulus recovery is more dominant in the long term. A healing index is developed based only on the fracture healing of asphalt binder, excluding the effect of viscoelastic recovery. It can be used to evaluate the true healing properties of different asphalt binders. Copyright © 2014 by ASTM International.

Integrated optimisation of surface roughness and tool performance when face milling 416 SS

Tool life is an important factor to be considered during the optimisation of a machining process since cutting parameters can be adjusted to optimise tool changing, reducing cost and time of production. Also the performance of a tool is directly linked to the generated surface roughness and this is important in cases where there are strict surface quality requirements. The prediction of tool life and the resulting surface roughness in milling operations has attracted considerable research efforts. The research reported herein is focused on defining the influence of milling cutting parameters such as cutting speed, feed rate and axial depth of cut, on three major tool performance parameters namely, tool life, material removal and surface roughness. The research is seeking to define methods that will allow the selection of optimal parameters for best tool performance when face milling 416 stainless steel bars. For this study the Taguchi method was applied in a special design of an orthogonal array that allows studying the entire parameter space with only a number of experiments representing savings in cost and time of experiments. The findings were that the cutting speed has the most influence on tool life and surface roughness and very limited influence on material removal. By last tool life can be judged either from tool life or volume of material removal.

Facile synthesis and proposed mechanism of α,ω‐oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane) by an SN2(i) nitrato displacement method in basic media

The synthesis of a novel heterocyclic–telechelic polymer, α,ω-oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane), is described. Infrared spectroscopy (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy have been used to confirm the successful synthesis, demonstrating the presence of the telechelic-oxetanyl moieties. Synthesis of the terminal functionalities has been achieved via displacement of nitrato groups, in a manner similar to that employed with other leaving groups such as azido, bromo, and nitro, initiated by nucleophiles. In the present case, displacement occurs on the ends of a nitrato-functionalized polymer driven by the formation of sodium nitrate, which is supported by the polar aprotic solvent N,N-dimethyl formamide. The formation of an alkoxide at the polymer chain ends is favored and allows internal back-biting to the nearest carbon bearing the nitrato group, intrinsically in an SN2(i) reaction, leading to α,ω-oxetanyl functionalization. The telechelic-oxetanyl moieties have the potential to be cross-linked by chemical (e.g., acidic) or radiative (e.g., ultraviolet) curing methods without the use of high temperatures, usually below 100°C. This type of material was designed for future use as a contraband simulant, whereby it would form the predominant constituent of elastomeric composites comprising rubbery polymer with small quantities of solids, typically crystals of contraband substances, such as explosives or narcotics. This method also provides an alternative approach to ring closure and synthesis of heterocycles.

A hiány újratermelése (The reproduction of shortage)

Sporadic lack of consumer articles, the housing shortage, disturbances of material supply, and shortages of investment goods and of labour may be traced back to a common main cause. Shortage is constantly reproduced by specific features of the economic mechanism. The first part of the article consists of micro-analysis, mainly of the productive enterprise. Efforts to increase production may run up against ceilings of three kinds: constraints on physical resources, constraints on demand, and the budget constraint on enterprises. It is an important feature of a system which of these constraints takes effect. Resource-constrained systems can be distinguished from demand-constrained ones here. In the former, production is limited by production bottlenecks, in the latter by buyer demand. The socialist economy in its "classical" form belongs to the former type. It is related to whether the budget constraint on the enterprise is "hard" or "soft". If hard, enterprise spending is limited by its financial scope, if soft (its losses offset almost automatically) its demand becomes almost insatiable. The second part performs a macro-analysis, showing the mechanism of "suction" with the aid of a hydraulic analogy. The enterprise sector "pumps away" reserves and surpluses of the system, mainly due to the "investment hunger" that appears in the wake of expansionist efforts. Finally the article discusses briefly the interrelations between shortage and inflation.

Preimplantation genetic diagnosis: Analysis of gene expression, nuclear DNA and cytoplasmic DNA

Preimplantation genetic diagnosis (PGD) following in vitro fertilization (IVF) offers couples at risk for transmitting genetic disorders the opportunity to identify affected embryos prior to replacement. In particular, embryo gender determination permits screening for X-linked diseases of unknown etiology. Analysis of embryos can be performed by polymerase chain reaction (PCR) amplification of material obtained by micromanipulation. This approach provides an alternative to the termination of an established pregnancy following chorionic villi sampling or amniocentesis. ^ Lately, the focus of preimplantation diagnosis and intervention has been shifting toward an attempt to correct cytoplasmic deficiencies. Accordingly, it is the aim of this investigation to develop methods to permit the examination of single cells or components thereof for clinical evaluation. In an attempt to lay the groundwork for precise therapeutic intervention for age related aneuploidy, transcripts encoding proteins believed to be involved in the proper segregation of chromosomes during human oocyte maturation were examined and quantified. Following fluorescent rapid cycle RT-PCR analysis it was determined that the concentration of cell cycle checkpoint gene transcripts decreases significantly as maternal age increases. Given the well established link between increasing maternal age and the incidence of aneuploidy, these results suggest that the degradation of these messages in aging oocytes may be involved with inappropriate chromosome separation during meiosis. ^ In order to investigate the cause of embryonic rescue observed following clinical cytoplasmic transfer procedures and with the objective of developing a diagnostic tool, mtDNA concentrations in polar bodies and subcellular components were evaluated. First, the typical concentration of mtDNA in human and mouse oocytes was determined by fluorescent rapid cycle PCR. Some disparity was noted between the copy numbers of individual cytoplasmic samples which may limit the use of the current methodology for the clinical assessment of the corresponding oocyte. ^

Improved sampling and detection of ignitable liquid residues and explosives by mass spectrometry and ion mobility spectrometry

Fire debris evidence is submitted to crime laboratories to determine if an ignitable liquid (IL) accelerant was used to commit arson. An ignitable liquid residue (ILR) may be difficult to analyze due to interferences, complex matrices, degradation, and low concentrations of analytes. Debris from an explosion and pre-detonated explosive compounds are not trivial to detect and identify due to sampling difficulties, complex matrices, and extremely low amounts (nanogram) of material present. The focus of this research is improving the sampling and detection of ILR and explosives through enhanced sensitivity, selectivity, and field portable instrumentation. Solid Phase MicroExtraction (SPME) enhanced the extraction of ILR by two orders of magnitude over conventional activated charcoal strip (ACS) extraction. Gas chromatography tandem mass spectrometry (GC/MS/MS) improved sensitivity of ILR by one order of magnitude and explosives by two orders of magnitude compared to gas chromatography mass spectrometry (GC/MS). Improvements in sensitivity were attributed to enhanced selectivity. An interface joining SPME to ion mobility spectrometry (IMS) has been constructed and evaluated to improve field detection of hidden explosives. The SPME-IMS interface improved the detection of volatile and semi-volatile explosive compounds and successfully adapted the IMS from a particle sampler into a vapor sampler. ^

Disease and hygiene in the construction of a nation: The public sphere, public space, and the private domain in Buenos Aires, 1871–1910

The maturation of the public sphere in Argentina during the late nineteenth and early twentieth centuries was a critical element in the nation-building process and the overall development of the modern state. Within the context of this evolution, the discourse of disease generated intense debates that subsequently influenced policies that transformed the public spaces of Buenos Aires and facilitated state intervention within the private domains of the city’s inhabitants. Under the banner of hygiene and public health, municipal officials thus Europeanized the nation’s capital through the construction of parks and plazas and likewise utilized the press to garner support for the initiatives that would remedy the unsanitary conditions and practices of the city. Despite promises to the contrary, the improvements to the public spaces of Buenos Aires primarily benefited the porteño elite while the efforts to root out disease often targeted working-class neighborhoods. The model that reformed the public space of Buenos Aires, including its socially differentiated application of aesthetic order and public health policies, was ultimately employed throughout the Argentine Republic as the consolidated political elite rolled out its national program of material and social development.

Systems Engineering Perspective of the Cruise Industry

The maturation of the cruise industry has led to increased competition which demands more efficient operations. Systems engineering, a discipline that studies complex organizations of material, people, and information, is traditionally only applied in the manufacturing sector; however, it can make significant contributions to service industries such as the cruise industry. The author describes this type of engineering, explores how it can be applied to the cruise industry, and presents two case studies demonstrating applications to the cruise industry luggage delivery process and the information technology help desk process. The results show that this approach can make the processes more productive and enhance profitability for the cruise lines.

An experimental study of micro-end-milling operations

Cutting tools less than 2mm diameter can be considered as micro-tool. Microtools are used in variety of applications where precision and accuracy are indispensable. In micro-machining operations, a small amount of material is removed and very small cutting forces are created. The small cross sectional area of the micro-tools drastically reduces their strength and makes their useful life short and unpredictable; so cutting parameters should be selected carefully to avoid premature tool breakage. The main objective of this study is to develop new techniques to select the optimal cutting conditions with minimum number of experiments and to evaluate the tool wear in machining operations. Several experimental setups were prepared and used to investigate the characteristics of cutting force and AE signals during the micro-end-milling of different materials including steel, aluminum and graphite electrodes. The proposed optimal cutting condition selection method required fewer experiments than conventional approaches and avoided premature tool breakage. The developed tool wear monitoring technique estimated the used tool life with ±10% accuracy from the machining data collected during the end-milling of non-metal materials.

Annotated record of the detailed examination of Mn nodules recovered from the VA04 expedition (R/V Valdivia) in the Pacific Ocean

Twenty-four manganese nodules from the surface of the sea floor and fifteen buried nodules were studied. With three exceptions, the nodules were collected from the area covered by Valdivia Cruise VA 04 some 1200 nautical miles southeast of Hawaii. Age determinations were made using the ionium method. In order to get a true reproduction of the activity distribution in the nodules, they were cut in half and placed for one month on nuclear emulsion plates to determine the alpha-activity of the ionium and its daughter products. Special methods of counting the alpha-tracks resolution to depth intervals of 0.125 mm. For the first time it was possible to resolve zones of rapid growth (impulse growth) with growth rates, s > 50 mm/106 yr and interruptions in growth. With few exceptions the average rate of growth of all nodules was surprisingly uniform at 4-9 mm/10 yr. No growth could be recognized radioactively in the buried nodules. One exceptional nodule has had recent impulse growth and, in the material formed, the ionium is not yet in equilibrium with its daughter products. Individual layers in one nodule from the Indian Ocean could be dated and an average time interval of t = 2600±400 yr was necessary to form one layer. The alternation between iron and manganese-rich parts of the nodules was made visible by colour differences resulting from special treatment of cut surfaces with HCl vapour. The zones of slow growth of one nodule are relatively enriched in iron. Earlier attempts to find paleomagnetic reversals in manganese nodules have been continued. Despite considerable improvement in areal resolution, reversals were not detected in the nodules studied. Comparisons of the surface structure, microstructure in section and the radiometric dating show that there are erosion surfaces and growth surfaces on the outer surfaces of the manganese nodules. The formation of cracks in the nodules was studied in particular. The model of age-dependent nodule shrinkage and cracking surprisingly indicates that the nodules break after exceeding a certain age and/or size. Consequently, the breaking apart of manganese nodules is a continuous process not of catastrophic or discontinuous origin. The microstructure of the nodules exhibits differences in the mechanism of accretion and accretion rate of material, shortly referred to as accretion form. Thus non-directional growth inside the nodules as well as a directional growth may be observed. Those nodules with large accretion forms have grown faster than smaller ones. Consequently, parallel layers indicate slow growth. The upper surfaces of the nodules, protruding into the bottom water appear to be more prone to growth disturbances than the lower surfaces, immersed in the sediment. Features of some nodules show, that as they develop, they neither turned nor rolled. Yet unknown is the mechanism that keeps the nodules at the surface during continuous sedimentation. All in all, the nodules remain the objects of their own distinctive problems. The hope of using them as a kind of history book still seems to be very remote.