A novel Mo-W interlayer approach for CVD diamond deposition on steel

Steel is the most widely used material in engineering for its cost/performance ratio and coatings are routinely applied on its surface to further improve its properties. Diamond coated steel parts are an option for many demanding industrial applications through prolonging the lifetime of steel parts, enhancement of tool performance as well as the reduction of wear rates. Direct deposition of diamond on steel using conventional chemical vapour deposition (CVD) processes is known to give poor results due to the preferential formation of amorphous carbon on iron, nickel and other elements as well as stresses induced from the significant difference in the thermal expansion coefficients of those materials. This article reports a novel approach of deposition of nanocrystalline diamond coatings on high-speed steel (M42) substrates using a multi-structured molybdenum (Mo) - tungsten (W) interlayer to form steel/Mo/Mo-W/W/diamond sandwich structures which overcome the adhesion problem related to direct magnetron sputtering deposition of pure tungsten. Surface, interface and tribology properties were evaluated to understand the role of such an interlayer structure. The multi-structured Mo-W interlayer has been proven to improve the adhesion between diamond films and steel substrates by acting as an effective diffusion barrier during the CVD diamond deposition.

Do work placements improve final year academic performance or do high-calibre students choose to do work placements?

This study investigates whether the completion of an optional sandwich work placement enhances student performance in final year examinations. Using Propensity Score Matching, our analysis departs from the literature by controlling for self-selection. Previous studies may have overestimated the impact of sandwich work placements on performance because it might be the case that high-calibre students choose to go on placement. Our results, utilising a large student data set, indicate that self-selection is present, but the effects of a placement on student performance still have an impact. This robust finding is found to be of a remarkably similar magnitude across two UK universities.

A Note on Univalent Functions with Finitely many Coefficients

MSC 2010: 30C45

Investigating ocular allergy:can we determine a better measurement?

Objective: Ocular allergy is a broad group of allergic conditions involving inflammation of the conjunctiva and the most common forms are seasonal allergic conjunctivitis (SAC; 90% of cases) and perennial allergic conjunctivitis (PAC; 5% of cases). The main symptom is ocular itching caused by mast cell degranulation leading to the release of histamine and other mediators such as tryptase. Tryptase is a neutral protease that is selectively concentrated in the secretory granules of human mast cells and has been shown to be a sensitive and specific marker of type I hypersensitivity reaction. The objective was to ascertain the best assay method for determining the tryptase levels in tear samples and whether this can be used to determine the efficacy of non-pharmacological treatments compared to no treatment or their combined effect with anti-allergic medication for SAC and PAC. Method: Thirty patients with a history of SAC were recruited into a randomised blind study during winter months when all the patients were asymptomatic. Suitability was determined by skin prick and conjunctival provocation tests. Patients were randomly assigned to either a non-pharmacological or a pharmacological Intervention group and received each test condition assigned to their group in a randomly assigned order. Symptoms were provoked by exposure to pollen in an environmental test chamber where the temperature, humidity and grass pollen levels were set to a high pollen count day. Tear samples were taken set intervals during the visit and then processed by enzyme linked immunosorbent assay (ELISA) for the detection of tryptase levels. Preliminary results: Results are still being analysed but the preliminary optimisation experiments tested four different ELISA systems; two indirect assays and two capture ‹sandwich› assays. The results suggest that in both sandwich assay systems non-specific binding occurred which could not be easily overcome. The indirect assay systems both showed specific reactions, and the sensitivity achieved was greater with the monoclonal than the polyclonal antibody. Using these findings the indirect assay system was optimised to provide a standardised system for measuring tryptase. Initial trials using human tear samples displayed tryptase levels between 23.1 and 175.1 ng/ml; levels which fall within the anticipated range for patients with SAC. Further statistical work is needed to determine whether tryptase levels vary between the treatments 75.

Investigating the ability of antibodies to recognize specific oxidized protein epitopes

There is a growing awareness that inflammatory diseases have an oxidative pathology, which can result in specific oxidation of amino acids within proteins. Antibody-based techniques for detecting oxidative posttranslational modifications (oxPTMs) are often used to identify the level of protein oxidation. There are many commercially available antibodies but some uncertainty to the potential level of cross reactivity they exhibit; moreover little information regarding the specific target epitopes is available. The aim of this work was to investigate the potential of antibodies to distinguish between select peptides with and without oxPTMs. Two peptides, one containing chlorotyrosine (DY-Cl-EDQQKQLC) and the other an unmodified tyrosine (DYEDQQKQLC) were synthesized and complementary anti-sera were produced in sheep using standard procedures. The anti-sera were tested using a half-sandwich ELISA and the anti-serum raised against the chloro-tyrosine containing peptide showed increased binding to the chlorinated peptide, whereas the control anti-serum bound similarly to both peptides. This suggested that antibodies can discriminate between similar peptide sequences with and without an oxidative modification. A peptide (STSYGTGC) and its variants with chlorotyrosine or nitrotyrosine were produced. The anti-sera showed substantially less binding to these alternative peptides than to the original peptides the anti-sera were produced against. Work is ongoing to test commercially available antibodies against the synthetic peptides as a comparison to the anti-sera produced in sheep. In conclusion, the antisera were able to distinguish between oxidatively modified and unmodified peptides, and two different sequences around the modification site.

Study of carbon nanotube film and shape memory alloys treatment for sensing and structural vibration control

Structural vibration control is of great importance. Current active and passive vibration control strategies usually employ individual elements to fulfill this task, such as viscoelastic patches for providing damping, transducers for picking up signals and actuators for inputting actuating forces. The goal of this dissertation work is to design, manufacture, investigate and apply a new type of multifunctional composite material for structural vibration control. This new composite, which is based on multi-walled carbon nanotube (MWCNT) film, is potentially to function as free layer damping treatment and strain sensor simultaneously. That is, the new material integrates the transducer and the damping patch into one element. The multifunctional composite was prepared by sandwiching the MWCNT film between two adhesive layers. Static sensing test indicated that the MWCNT film sensor resistance changes almost linearly with the applied load. Sensor sensitivity factors were comparable to those of the foil strain gauges. Dynamic test indicated that the MWCNT film sensor can outperform the foil strain gage in high frequency ranges. Temperature test indicated the MWCNT sensor had good temperature stability over the range of 237 K-363 K. The Young’s modulus and shear modulus of the MWCNT film composite were acquired by nanoindentation test and direct shear test, respectively. A free vibration damping test indicated that the MWCNT composite sensor can also provide good damping without adding excessive weight to the base structure. A new model for sandwich structural vibration control was then proposed. In this new configuration, a cantilever beam covered with MWCNT composite on top and one layer of shape memory alloy (SMA) on the bottom was used to illustrate this concept. The MWCNT composite simultaneously serves as free layer damping and strain sensor, and the SMA acts as actuator. Simple on-off controller was designed for controlling the temperature of the SMA so as to control the SMA recovery stress as input and the system stiffness. Both free and forced vibrations were analyzed. Simulation work showed that this new configuration for sandwich structural vibration control was successful especially for low frequency system.

Global compilation of benthic data sets I

Approaches to quantify the organic carbon accumulation on a global scale generally do not consider the small-scale variability of sedimentary and oceanographic boundary conditions along continental margins. In this study, we present a new approach to regionalize the total organic carbon (TOC) content in surface sediments (<5 cm sediment depth). It is based on a compilation of more than 5500 single measurements from various sources. Global TOC distribution was determined by the application of a combined qualitative and quantitative-geostatistical method. Overall, 33 benthic TOC-based provinces were defined and used to process the global distribution pattern of the TOC content in surface sediments in a 1°x1° grid resolution. Regional dependencies of data points within each single province are expressed by modeled semi-variograms. Measured and estimated TOC values show good correlation, emphasizing the reasonable applicability of the method. The accumulation of organic carbon in marine surface sediments is a key parameter in the control of mineralization processes and the material exchange between the sediment and the ocean water. Our approach will help to improve global budgets of nutrient and carbon cycles.

Geochemistry of Southern Ocean sediments

Reconstructing past detrital flux and provenance in the Southern Ocean provides information about changes in source regions associated with climate variations and transport pathways. We present a Last Glacial Maximum (LGM) to Holocene comparison of 230Th normalised fluxes combined with sediment provenance data (Pb, Nd and Sr isotopes) from a latitudinal core transect in the eastern Atlantic sector of the Southern Ocean (ODP Leg 177 cores). We compare the radiogenic isotopic composition (IC) of detritus in these cores to that of cores proximal to potential source areas. We observe a well-defined latitudinal Holocene gradient in both detrital flux and provenance of sediment. High detrital fluxes in the north are associated with terrigenous material derived from southern Africa, while low detrital fluxes in the south are associated with supply from southern South America, West Antarctica and the South Sandwich Islands. The data suggest that this well-defined Holocene gradient in detrital flux and sediment provenance is controlled by the flow of the Antarctic Circumpolar Current (ACC) and the position of its frontal zones. The LGM is characterised by 2 to 6 times higher than modern detrital fluxes at most ODP Leg 177 sites. The LGM detrital fluxes do not show a latitudinal trend and suggest a greater supply of glaciogenic detritus sourced from southern South America. Glacial Patagonian outwash sediments (< 5 µm fraction) were analysed and compared to the bulk compositions of the marine sediments. The Pb IC of the Patagonian sediments is very similar to the glacial IC of sediments in the Scotia Sea and at ~ 49° S latitude in the eastern Atlantic sector. We propose that the glacial IC of sediments is controlled by increased delivery of Patagonian detritus initially supplied by glaciers and then transported at depth via the ACC.

Sedimentation rates and geochemical analysis of surface sediments from the South Atlantic

Extensive investigations of sedimentary barium were performed in the southern South Atlantic in order to assess the reliability of the barium signal in Antarctic sediments as a proxy for paleoproductivity. Maximum accumulation rates of excess barium were calculated for the Antarctic zone south of the polar front where silica accumulates at high rates. The correspondence between barium and opal supports the applicability of barium as a proxy for productivity. Within the Antarctic zone north of today's average sea ice maximum, interglacial vertical rain rates of excess barium are high, with a maximum occurring during the last deglaciation and early Holocene and during oxygen isotope chronozone 5.5. During these periods, the maximum silica accumulation was supposedly located south of the polar front. Glacial paleoproductivity, instead, was low within the Antarctic zone. North of the polar front, significantly higher barium accumulation occurs during glacial times. The vertical rain rates, however, are as high as in the glacial Antarctic zone. Therefore there was no evidence for an increased productivity in the glacial Southern Ocean.

Physical properties measured on sediment cores from high latitudes

This collection of 359 data sets represents raw data of physical properties measurements on Polarstern sediment cores from both polar oceans, sampled and measured between 1985 and 1995.

Estimation of sea surface temperature from sediment core PS1768-8

The quantitative diatom analysis of 218 surface sediment samples recovered in the Atlantic and western Indian sector of the Southern Ocean is used to define a base of reference data for paleotemperature estimations from diatom assemblages using the Imbrie and Kipp transfer function method. The criteria which justify the exclusion of samples and species out of the raw data set in order to define a reference database are outlined and discussed. Sensitivity tests with eight data sets were achieved evaluating the effects of overall dominance of single species, different methods of species abundance ranking, and no-analog conditions (e.g., Eucampia Antarctica) on the estimated paleotemperatures. The defined transfer functions were applied on a sediment core from the northern Antarctic zone. Overall dominance of Fragilariopsis kerguelensis in the diatom assemblages resulted in a close affinity between paleotemperature curve and relative abundance pattern of this species downcore. Logarithmic conversion of counting data applied with other ranking methods in order to compensate the dominance of F. kerguelensis revealed the best statistical results. A reliable diatom transfer function for future paleotemperature estimations is presented.

Accumulation rates of bulk sediment and opal in surface sediments of the South Atlantic

A set of 114 samples from the sediment surface of the Atlantic, eastern Pacific and western Indian sectors of the Southern Ocean has been analyzed for 230Th and biogenic silica. Maps of opal content, Th-normalized mass flux, and Th-normalized biogenic opal flux into the sediment have been derived. Significant differences in sedimentation patterns between the regions can be detected. The mean bulk vertical fluxes integrated into the sediment in the open Southern Ocean are found in a narrow range from 2.9 g/m**2 yr (Eastern Weddell Gyre) to 15.8 g/m**2 yr (Indian sector), setting upper and lower limits to the vertically received fraction of open ocean sediments. The silica flux to sediments of the Atlantic sector of the Southern Ocean is found to be 4.2 ± 1.4 * 10**11 mol/yr, just one half of the last estimate. This adjustment represents 6% of the output term in the global marine silica budget.

Annotated record of the detailed examination of Mn deposits from R/V Eltanin Cruise 5 stations

Cores, submarine photography and dredges described in this report were taken during the R/V Eltanin Cruise 5 in 1962 by the Department of Geology, Florida State University. Cores and dredges were recovered for 31 stations and are available at the Antarctic Research Facility, Florida State University for sampling and study.

Sea-surface temperature and sea ice distribution of the Southern Ocean at the EPILOG Last Glacial Maximum

Based on the quantitative study of diatoms and radiolarians, summer sea-surface temperature (SSST) and sea ice distribution were estimated from 122 sediment core localities in the Atlantic, Indian and Pacific sectors of the Southern Ocean to reconstruct the last glacial environment at the EPILOG (19.5-16.0 ka or 23 000-19 000 cal yr. B.P.) time-slice. The statistical methods applied include the Imbrie and Kipp Method, the Modern Analog Technique and the General Additive Model. Summer SSTs reveal greater surface-water cooling than reconstructed by CLIMAP (Geol. Soc. Am. Map Chart. Ser. MC-36 (1981) 1), reaching a maximum (4-5 °C) in the present Subantarctic Zone of the Atlantic and Indian sector. The reconstruction of maximum winter sea ice (WSI) extent is in accordance with CLIMAP, showing an expansion of the WSI field by around 100% compared to the present. Although only limited information is available, the data clearly show that CLIMAP strongly overestimated the glacial summer sea ice extent. As a result of the northward expansion of Antarctic cold waters by 5-10° in latitude and a relatively small displacement of the Subtropical Front, thermal gradients were steepened during the last glacial in the northern zone of the Southern Ocean. Such reconstruction may, however, be inapposite for the Pacific sector. The few data available indicate reduced cooling in the southern Pacific and give suggestion for a non-uniform cooling of the glacial Southern Ocean.

Benthic organic carbon flux and oxygen penetration depth in the Southern Ocean

For the investigation of organic carbon fluxes reaching the seafloor, oxygen microprofiles were measured at 145 sites in different sub-regions of the Southern Ocean. At eleven sites, an in situ oxygen microprofiler was deployed for the measurement of oxygen profiles and the calculation of organic carbon fluxes. At four sites, both in situ and ex situ data were determined for high latitudes. Based on this dataset as well as on previous published data, a relationship was established for the estimation of fluxes derived by ex situ measured O2 profiles. The fluxes of labile organic matter range from 0.5 to 37.1 mgC m**2/day. The high values determined by in situ measurements were observed in the Polar Front region (water depth of more than 4290 m) and are comparable to organic matter fluxes observed for high-productivity, upwelling areas like off West Africa. The oxygen penetration depth, which reflects the long-term organic matter flux to the sediment, was correlated with assemblages of key diatom species. In the Scotia Sea (~3000 m water depth), oxygen penetration depths of less than 15 cm were observed, indicating high benthic organic carbon fluxes. In contrast, the oxic zone extends down to several decimeters in abyssal sediments of the Weddell Sea and the southeastern South Atlantic. The regional pattern of organic carbon fluxes derived from micro-sensor data suggest that episodic and seasonal sedimentation pulses are important for the carbon supply to the seafloor of the deep Southern Ocean.