Origin of Ferroelastic domains in Free-Standing Single Crystal Ferroelectric Films

The origin of the unusual 90 degrees ferroelectric/ferroelastic domains, consistently observed in recent studies on mesoscale and nanoscale free-standing single crystals of BaTiO3 [Schilling , Phys. Rev. B 74, 024115 (2006); Schilling , Nano Lett. 7, 3787 (2007)], has been considered. A model has been developed which postulates that the domains form as a response to elastic stress induced by a surface layer which does not undergo the paraelectric-ferroelectric cubic-tetragonal phase transition. This model was found to accurately account for the changes in domain periodicity as a function of size that had been observed experimentally. The physical origin of the surface layer might readily be associated with patterning damage, seen in experiment; however, when all evidence of physical damage is removed from the BaTiO3 surfaces by thermal annealing, the domain configuration remains practically unchanged. This suggests a more intrinsic origin, such as the increased importance of surface tension at small dimensions. The effect of surface tension is also shown to be proportional to the difference in hardness between the surface and the interior of the ferroelectric. The present model for surface-tension induced twinning should also be relevant for finely grained or core-shell structured ceramics.

Spatial characterization of salt accumulation in early stage limestone weathering using probe permeametry

This research characterizes the weathering of natural building stone using an unsteady-state portable probe permeameter. Variations between the permeability properties of fresh rock and the same rocks after the early stages of a salt weathering simulation are used to examine the effects of salt accumulation on spatial variations in surface rock permeability properties in two limestones from Spain. The Fraga and Tudela limestones are from the Ebro basin and are of Miocene age. Both stone types figure largely in the architectural heritage of Spain and, in common with many other building limestones, they are prone to physical damage from salt crystallization in pore spaces. To examine feedbacks associated with salt accumulation during the early stages of this weathering process, samples of the two stone types were subjected to simulated salt weathering under laboratory conditions using magnesium sulphate and sodium chloride at concentrations of 5% and 15%. Permeability mapping and statistical analysis (aspatial statistics and spatial prediction) before and after salt accumulation are used to assess changes in the spatial variability of permeability and to correlate these changes with salt movement, porosity change, potential rock deterioration and textural characteristics. Statistical analyses of small-scale permeability measurements are used to evaluate the drivers for decay and hence aid the prediction of the weathering behaviour of the two limestones.

Changing climate, changing process: implications for salt transportation and weathering within building sandstones in the UK

Salt weathering is a crucial process that brings about a change in stone, from the scale of landscapes to stone outcrops and natural building stone facades. It is acknowledged that salt weathering is controlled by fluctuations in temperature and moisture, where repeated oscillations in these parameters can cause re-crystallisation, hydration/de-hydration of salts, bringing about stone surface loss in the form of, for example, granular disaggregation, scaling, and multiple flaking. However, this ‘traditional’ view of how salt weathering proceeds may need to be re-evaluated in the light of current and future climatic trends. Indeed, there is considerable scope for the investigation of consequences of climate change on geomorphological processes in general. Building on contemporary research on the ‘deep wetting’ of natural building stones, it is proposed that (as stone may be wetter for longer), ion diffusion may become a more prominent mechanism for the mixing of molecular constituents, and a shift in focus from physical damage to chemical change is suggested. Data from ion diffusion cell experiments are presented for three different sandstone types, demonstrating that salts may diffuse through porous stone relatively rapidly (in comparison to, for example, dense concrete). Pore water from stones undergoing diffusion experiments was extracted and analysed. Factors controlling ion diffusion
relating to ‘time of wetness’ within stones are discussed, (continued saturation, connectivity of pores, mineralogy, behaviour of salts, sedimentary structure), and potential changes in system dynamics as a result of climate change are addressed. System inputs may change in terms of increased moisture input, translating into a greater depth of wetting front. Salts are likely to be ‘stored’ differently in stones, with salt being in solution for longer periods (during prolonged winter wetness). This has myriad implications in terms of the movement of ions by diffusion and the potential for chemical change in the stone (especially in more mobile constituents), leading to a weakening of the stone matrix/grain boundary cementing. The ‘output’ may be mobilisation and precipitation of elements leading to, for example, uneven cementing in the stone. This reduced strength of the stone, or compromised ability of the stone to absorb stress, is likely to make crystallisation a more efficacious mechanism of decay when it does occur. Thus, a delay in the onset of crystallisation while stonework is wet does not preclude exaggerated or accelerated material loss when it finally happens.

The use and meanings of 'time of wetness' in understanding stone decay

Moisture is a well documented, and crucial, control on the nature of stone decay. The term time of wetness has frequently been adopted to describe how long a stone block is wet, with a view to understanding the impact of this on decay processes. Although this term has proved conceptually useful, it has been used in different ways, by different groups to mean mean quite different things. For example, the time of wetness for a stone block surface (the traditional understanding) may be quite different from that of a block interior, controlled by the different dynamics of wetting and drying in those zones. Thus, surface wetting will occur regularly (sometimes swiftly followed by drying, depending on the time of year), with block interior wetting requiring the accumulation of surface moisture to penetrate to depth (more likely in autumn and winter months), and drying out much more slowly. This relatively new but important perspective, framed in the context of climate change, is crucial to understanding the length of time stone may remain damp at depth following a period of prolonged precipitation. The nature and speed of drying is also relevant in quantifying time of wetness of both surfaces and the interior of building stones.
These ideas related to time of wetness have implications for decay processes, specifically how a prolonged time of deep wetness may re-focus the emphasis of salt weathering in natural building stones toward chemical action. Literature on chemical change is discussed, suggesting that chemical change occurring during periods of prolonged wetness is likely to be significant in itself, with implications for weakening the stone (in terms of, for example, cement dissolution or grain boundary weakening) and exacerbating physical damage from salt crystallisation when blocks finally dry out.

Stateful Intrusion Detection for IEC 60870-5-104 SCADA Security

Cyber threats in Supervisory Control and Data Acquisition (SCADA) systems have the potential to render physical damage and jeopardize power system operation, safety and stability. SCADA systems were originally designed with little consideration of escalating cyber threats and hence the problem of how to develop robust intrusion detection technologies to tailor the requirements of SCADA is an emerging topic and a big challenge. This paper proposes a stateful Intrusion Detection System (IDS) using a Deep Packet Inspection (DPI) method to improve the cyber-security of SCADA systems using the IEC 60870-5-104 protocol which is tailored for basic telecontrol communications. The proposed stateful protocol analysis approach is presented that is designed specifically for the IEC 60870-5-104 protocol. Finally, the novel intrusion detection approach are implemented and validated.

Do Changes in Current Flow as a Result of Arrays of Tidal Turbines Have an Effect on Benthic Communities?

Arrays of tidal energy converters have the potential to provide clean renewable energy for future generations. Benthic communities may, however, be affected by changes in current speeds resulting from arrays of tidal converters located in areas characterised by strong currents. Current speed, together with bottom type and depth, strongly influence benthic community distributions; however the interaction of these factors in controlling benthic dynamics in high energy environments is poorly understood. The Strangford Lough Narrows, the location of SeaGen, the world’s first single full-scale, grid-compliant tidal energy extractor, is characterised by spatially heterogenous high current flows. A hydrodynamic model was used to select a range of benthic community study sites that had median flow velocities between 1.5–2.4 m/s in a depth range of 25–30 m. 25 sites were sampled for macrobenthic community structure using drop down video survey to test the sensitivity of the distribution of benthic communities to changes in the flow field. A diverse range of species were recorded which were consistent with those for high current flow environments and corresponding to very tide-swept faunal communities in the EUNIS classification. However, over the velocity range investigated, no changes in benthic communities were observed. This suggested that the high physical disturbance associated with the high current flows in the Strangford Narrows reflected the opportunistic nature of the benthic species present with individuals being continuously and randomly affected by turbulent forces and physical damage. It is concluded that during operation, the removal of energy by marine tidal energy arrays in the far-field is unlikely to have a significant effect on benthic communities in high flow environments. The results are of major significance to developers and regulators in the tidal energy industry when considering the environmental impacts for site licences.

Sandstone response to salt weathering following simulated fire damage: a comparison of furnace heating and fire.

Fire has long been recognized as an agent of rock weathering. Our understanding of the impact of fire on stone comes either from early anecdotal evidence, or from more recent laboratory simulation studies, using furnaces to simulate the effects of fire. This paper suggests that knowledge derived from simulated heating experiments is based on the preconceptions of the experiment designer – when using a furnace to simulate fire, the operator decides on the maximum temperature and the duration of the experiment. These are key factors in determining the response of the stone to fire, and if these are removed from realworld observations then knowledge based on these simulations must be questioned. To explore the differences between heating sandstone in a furnace and a real fire, sample blocks of Peakmoor Sandstone were subjected to different stress histories in combination (lime rendering and removal, furnace heating or fire, frost and salt weathering). Block response to furnace heating and fire is discussed, with emphasis placed on the non-uniformity of the fire and of block response to fire in contrast to the uniform response to surface heating in a furnace. Subsequent response to salt weathering (by a 10% solution of sodium chloride and magnesium sulphate) was then monitored by weight loss. Blocks that had experienced fire showed a more unpredictable response to salt weathering than those that had undergone furnace heating – spalling of corners and rapid catastrophic weight loss were evidenced in blocks that had been subjected to fire, after periods of relative quiescence. An important physical side-effect of the fire was soot accumulation, which created a waxy, relatively impermeable layer on some blocks. This layer repelled water and hindered salt ingress, but eventually detached when salt, able to enter the substrate through more permeable areas, concentrated and crystallized behind it, resulting in rapid weight loss and accelerated decay. Copyright ©2007 John Wiley & Sons, Ltd.

Spatio-temporal analysis of DNA damage repair using the X-ray microbeam

Cellular response to radiation damage is made by a complex network of pathways and feedback loops whose spatiotemporal organization is still unclear despite its decisive role in determining the fate of the damaged cell. The single-cell approach and the high spatial resolution offered by microbeams provide the perfect tool to study and quantify the dynamic processes associated with the induction and repair of DNA damage. The soft X-ray microbeam has been used to follow the development of radiation induced foci in live cells by monitoring their size and intensity as a function of dose and time using yellow fluorescent protein (YFP) tagging techniques. Preliminary data indicate a delayed and linear rising of the intensity signal indicating a slow kinetic for the accumulation of DNA repair protein 53BP1. A slow and limited foci diffusion has also been observed. Further investigations are required to assess whatever such diffusion is consistent with a random walk pattern or if it is the result of a more structured lesion processing phenomenon. In conclusion, our data indicates that the use of microbeams coupled to live cell microscopy represent a sophisticated approach for visualizing and quantifying the dynamics changes of DNA proteins at the damaged sites.

Experimental setup and first measurement of DNA damage induced along and around an antiproton beam

Radiotherapy employs ionizing radiation to induce lethal DNA lesions in cancer cells while minimizing damage to healthy tissues. Due to their pattern of energy deposition, better therapeutic outcomes can, in theory, be achieved with ions compared to photons. Antiprotons have been proposed to offer a further enhancement due to their annihilation at the end of the path. The work presented here aimed to establish and validate an experimental procedure for the quantification of plasmid and genomic DNA damage resulting from antiproton exposure. Immunocytochemistry was used to assess DNA damage in directly and indirectly exposed human fibroblasts irradiated in both plateau and Bragg peak regions of a 126 MeV antiproton beam at CERN. Cells were stained post irradiation with an anti-gamma-H2AX antibody. Quantification of the gamma-H2AX foci-dose relationship is consistent with a linear increase in the Bragg peak region. A qualitative analysis of the foci detected in the Bragg peak and plateau region indicates significant differences highlighting the different severity of DNA lesions produced along the particle path. Irradiation of desalted plasmid DNA with 5 Gy antiprotons at the Bragg peak resulted in a significant portion of linear plasmid in the resultant solution.

Residual stress due to curing can initiate damage in porous bone cement: experimental and theoretical evidence

Residual stress due to shrinkage of polymethylmethacrylate bone cement after polymerisation is possibly one factor capable of initiating cracks in the mantle of cemented hip replacements. No relationship between residual stress and observed cracking of cement has yet been demonstrated. To investigate if any relationship exists, a physical model has been developed which allows direct observation of damage in the cement layer on the femoral side of total hip replacement. The model contains medial and lateral cement layers between a bony surface and a metal stem; the tubular nature of the cement mantle is ignored. Five specimens were prepared and examined for cracking using manual tracing of stained cracks, observed by transmission microscopy: cracks were located and measured using image analysis. A mathematical approach for the prediction of residual stress due to shrinkage was developed which uses the thermal history of the material to predict when stress-locking occurs, and estimates subsequent thermal stress. The residual stress distribution of the cement layer in the physical model was then calculated using finite element analysis. Results show maximum tensile stresses normal to the observed crack directions, suggesting a link between residual stress and preload cracking. The residual stress predicted depends strongly on the definition of the reference temperature for stress-locking. The highest residual stresses (4-7 MPa) are predicted for shrinkage from maximum temperature, in this case, magnitudes are sufficiently high to initiate cracks when the influence of stress raisers such as pores or interdigitation at the bone/cement interface are taken into account (up to 24 MPa when calculating stress around a pore according to the method of Harrigan and Harris (J. Biomech. 24(11) (1991) 1047-1058)). We conclude that the damage accumulation failure scenario begins before weight-bearing due to cracking induced by residual stress around pores or stress raisers. (C) 2002 Elsevier Science Ltd. All rights reserved.

IR laser desorption of oligonucleotides A novel gas phase target for radiation damage studies

The desorption of oligonucleotides by 3 mu m laser irradiation has been studied by laser induced fluorescence imaging of the resulting gas phase plumes. Fitting of the plume data has been achieved by using a modified Maxwell Boltzmann distribution which incorporates a range of stream velocities. Spatial density profiles, velocities and temperature variation have been determined from these fits indicating that the oligonucleotide plume only achieves a partial thermal relaxation. This laser desorption technique may provide a means of overcoming the limited mass range of gas phase biomolecules available from thermal evaporation techniques.

Nonadiabatic forces in ion-solid interactions:The initial stages of radiation damage

The Born-Oppenheimer approximation is the keystone for molecular dynamics simulations of radiation damage processes; however, actual materials response involves nonadiabatic energy exchange between nuclei and electrons. In this work, time dependent density functional theory is used to calculate the electronic excitations produced by energetic protons in Al. We study the influence of these electronic excitations on the interatomic forces and find that they differ substantially from the adiabatic case, revealing a nontrivial connection between electronic and nuclear stopping that is absent in the adiabatic case. These results unveil new effects in the early stages of radiation damage cascades.

DNA damage responses following exposure to modulated radiation fields

During the delivery of advanced radiotherapy treatment techniques modulated beams are utilised to increase dose conformity across the target volume. Recent investigations have highlighted differential cellular responses to modulated radiation fields particularly in areas outside the primary treatment field that cannot be accounted for by scattered dose alone. In the present study, we determined the DNA damage response within the normal human fibroblast AG0-1522B and the prostate cancer cell line DU-145 utilising the DNA damage assay. Cells plated in slide flasks were exposed to 1 Gy uniform or modulated radiation fields. Modulated fields were delivered by shielding 25%, 50% or 75% of the flask during irradiation. The average number of 53BP1 or ?H2AX foci was measured in 2 mm intervals across the slide area. Following 30 minutes after modulated radiation field exposure an increase in the average number of foci out-of-field was observed when compared to non-irradiated controls. In-field, a non-uniform response was observed with a significant decrease in the average number of foci compared to uniformly irradiated cells. Following 24 hrs after exposure there is evidence for two populations of responding cells to bystander signals in-and out-of-field. There was no significant difference in DNA damage response between 25%, 50% or 75% modulated fields. The response was dependent on cellular secreted intercellular signalling as physical inhibition of intercellular communication abrogated the observed response. Elevated residual DNA damage observed within out-of-field regions decreased following addition of an inducible nitric oxide synthase inhibitor (Aminoguanidine). These data show, for the first time, differential DNA damage responses in-and out-of-field following modulated radiation field delivery. This study provides further evidence for a role of intercellular communication in mediating cellular radiobiological response to modulated radiation fields and may inform the refinement of existing radiobiological models for the optimization of advanced radiotherapy treatment plans. © 2012 Trainor et al.