Preliminary approach to neutron instrument selecction at ESSB-Bilbao based on experience at ISIS molecular spectroscopy group

Collaborative efforts between the Neutronics and Target Design Group at the Instituto de Fusión Nuclear and the Molecular Spectroscopy Group at the ISIS Pulsed Neutron and Muon Source date back to 2012 in the context of the ESS-Bilbao project. The rationale for these joint activities was twofold, namely: to assess the realm of applicability of the low-energy neutron source proposed by ESS-Bilbao - for details; and to explore instrument capabilities for pulsed-neutron techniques in the range 0.05-3 ms, a time range where ESS-Bilbao and ISIS could offer a significant degree of synergy and complementarity. As part of this collaboration, J.P. de Vicente has spent a three-month period within the ISIS Molecular Spectroscopy Group, to gain hands-on experience on the practical aspects of neutron-instrument design and the requisite neutron-transport simulations. To date, these activities have resulted in a joint MEng thesis as well as a number of publications and contributions to national and international conferences. Building upon these previous works, the primary aim of this report is to provide a self-contained discussion of general criteria for instrument selection at ESS-Bilbao, the first accelerator-driven, low-energy neutron source designed in Spain. To this end, Chapter 1 provides a brief overview of the current design parameters of the accelerator and target station. Neutron moderation is covered in Chapter 2, where we take a closer look at two possible target-moderator-reflector configurations and pay special attention to the spectral and temporal characteristics of the resulting neutron pulses. This discussion provides a necessary starting point to assess the operation of ESSB in short- and long-pulse modes. These considerations are further explored in Chapter 3, dealing with the primary characteristics of ESS-Bilbao as a short- or long-pulse facility in terms of accessible dynamic range and spectral resolution. Other practical aspects including background suppression and the use of fast choppers are also discussed. The guiding principles introduced in the first three chapters are put to use in Chapter 4 where we analyse in some detail the capabilities of a small-angle scattering instrument, as well as how specific scientific requirements can be mapped onto the optimal use of ESS-Bilbao for condensed-matter research. Part 2 of the report contains additional supporting documentation, including a description of the ESSB McStas component, a detailed characterisation of moderator response and neutron pulses, and estimates ofparameters associated with the design and operation of neutron choppers. In closing this brief foreword, we wish to thank both ESS-Bilbao and ISIS for their continuing encouragement and support along the way.

Models for internal quality sorting of fruit, based on time-domain laser reflectance spectroscopy (TDRS).

Non-destructive measurement of fruit quality has been an important objective through recent years (Abbott, 1999). Near infrared spectroscopy (NIR) is applicable to the cuantification of chemicals in foods and NIK "laser spectroscopy" can be used to estimate the firmness of fruits. However, die main limitation of current optical techniques that measure light transmission is that they do not account for the coupling between absorption and scattering inside the tissue, when quantifying the intensity o f reemitted light. The solution o f this l i m i t a t i o n was the goal o f the present work.

Nondestructive quality evaluation and monitoring of Braeburn apples by Spatially Resolved Spectroscopy.

Contact Spatially Resolved Spectroscopy (SRS) measurements by means of a fiber-optics probe were employed for nondestructive assessment and monitoring of Braeburn apples during shelflife storage. SRS measurements and estimation of optical properties were calibrated and validated by means of liquid optical phantoms with known optical properties and a metamodeling method. The acquired optical properties (absorption and reduced scattering coefficients) for the apples during shelf-life storage were found to provide useful information for nondestructive evaluation of apple quality attributes (firmness and SSC) and for monitoring the changes in their microstructure and chemical composition. On-line SRS measurement was achieved by mounting the SRS probe over a conveyor system

Measuring the critical resolved shear stresses in Mg alloys by instrumented nanoindentation

One of the main limiting factors in the development of new magnesium (Mg) alloys with enhanced mechanical behavior is the need to use vast experimental campaigns for microstructure and property screening. For example, the influence of new alloying additions on the critical resolved shear stresses (CRSSs) is currently evaluated by a combination of macroscopic single-crystal experiments and crystal plasticity finite-element simulations (CPFEM). This time-consuming process could be considerably simplified by the introduction of high-throughput techniques for efficient property testing. The aim of this paper is to propose a new and fast, methodology for the estimation of the CRSSs of hexagonal close-packed metals which, moreover, requires small amounts of material. The proposed method, which combines instrumented nanoindentation and CPFEM modeling, determines CRSS values by comparison of the variation of hardness (H) for different grain orientations with the outcome of CPFEM. This novel approach has been validated in a rolled and annealed pure Mg sheet, whose H variation with grain orientation has been successfully predicted using a set of CRSSs taken from recent crystal plasticity simulations of single-crystal experiments. Moreover, the proposed methodology has been utilized to infer the effect of the alloying elements of an MN11 (Mg–1% Mn–1% Nd) alloy. The results support the hypothesis that selected rare earth intermetallic precipitates help to bring the CRSS values of basal and non-basal slip systems closer together, thus contributing to the reduced plastic anisotropy observed in these alloys

The two-dimensional IR nonlinear spectroscopy of a cyclic penta-peptide in relation to its three-dimensional structure

A form of two-dimensional (2D) vibrational spectroscopy, which uses two ultrafast IR laser pulses, is used to examine the structure of a cyclic penta-peptide in solution. Spectrally resolved cross peaks occur in the off-diagonal region of the 2D IR spectrum of the amide I region, analogous to those in 2D NMR spectroscopy. These cross peaks measure the coupling between the different amide groups in the structure. Their intensities and polarizations relate directly to the three-dimensional structure of the peptide. With the help of a model coupling Hamiltonian, supplemented by density functional calculations, the spectra of this penta-peptide can be regenerated from the known solution phase structure. This 2D-IR measurement, with an intrinsic time resolution of less than 1 ps, could be used in all time regimes of interest in biology.

Ultra-fast excited state dynamics in green fluorescent protein: multiple states and proton transfer.

The green fluorescent protein (GFP) of the jellyfish Aequorea Victoria has attracted widespread interest since the discovery that its chromophore is generated by the autocatalytic, posttranslational cyclization and oxidation of a hexapeptide unit. This permits fusion of the DNA sequence of GFP with that of any protein whose expression or transport can then be readily monitored by sensitive fluorescence methods without the need to add exogenous fluorescent dyes. The excited state dynamics of GFP were studied following photo-excitation of each of its two strong absorption bands in the visible using fluorescence upconversion spectroscopy (about 100 fs time resolution). It is shown that excitation of the higher energy feature leads very rapidly to a form of the lower energy species, and that the excited state interconversion rate can be markedly slowed by replacing exchangeable protons with deuterons. This observation and others lead to a model in which the two visible absorption bands correspond to GFP in two ground-state conformations. These conformations can be slowly interconverted in the ground state, but the process is much faster in the excited state. The observed isotope effect suggests that the initial excited state process involves a proton transfer reaction that is followed by additional structural changes. These observations may help to rationalize and motivate mutations that alter the absorption properties and improve the photo stability of GFP.

Pulse phase-coherent timing and spectroscopy of CXOU J164710.2−45521 outbursts

We present a long-term phase-coherent timing analysis and pulse-phase resolved spectroscopy for the two outbursts observed from the transient anomalous X-ray pulsar CXOU J164710.2−455216. For the first outburst we used 11 Chandra and XMM–Newton observations between 2006 September and 2009 August, the longest baseline yet for this source. We obtain a coherent timing solution with P = 10.61065583(4) s, Ṗ = 9.72(1) × 10−13 s s−1 and P̈ = –1.05(5) × 10−20 s s−2. Under the standard assumptions this implies a surface dipolar magnetic field of ∼1014 G, confirming this source as a standard B magnetar. We also study the evolution of the pulse profile (shape, intensity and pulsed fraction) as a function of time and energy. Using the phase-coherent timing solution we perform a phase-resolved spectroscopy analysis, following the spectral evolution of pulse-phase features, which hints at the physical processes taking place on the star. The results are discussed from the perspective of magnetothermal evolution models and the untwisting magnetosphere model. Finally, we present similar analysis for the second, less intense, 2011 outburst. For the timing analysis we used Swift data together with 2 XMM–Newton and Chandra pointings. The results inferred for both outbursts are compared and briefly discussed in a more general framework.

Orbital phase-resolved spectroscopy of 4U 1538−52 with MAXI

Context. 4U 1538−52, an absorbed high mass X-ray binary with an orbital period of ~3.73 days, shows moderate orbital intensity modulations with a low level of counts during the eclipse. Several models have been proposed to explain the accretion at different orbital phases by a spherically symmetric stellar wind from the companion. Aims. The aim of this work is to study both the light curve and orbital phase spectroscopy of this source in the long term. In particular, we study the folded light curve and the changes in the spectral parameters with orbital phase to analyse the stellar wind of QV Nor, the mass donor of this binary system. Methods. We used all the observations made from the Gas Slit Camera on board MAXI of 4U 1538−52 covering many orbits continuously. We obtained the good interval times for all orbital phase ranges, which were the input for extracting our data. We estimated the orbital period of the system and then folded the light curves, and we fitted the X-ray spectra with the same model for every orbital phase spectrum. We also extracted the averaged spectrum of all the MAXI data available. Results. The MAXI spectra in the 2–20 keV energy range were fitted with an absorbed Comptonisation of cool photons on hot electrons. We found a strong orbital dependence of the absorption column density but neither the fluorescence iron emission line nor low energy excess were needed to fit the MAXI spectra. The variation in the spectral parameters over the binary orbit were used to examine the mode of accretion onto the neutron star in 4U 1538−52. We deduce a best value of Ṁ/v∞ = 0.65 × 10-9M⊙ yr-1/ (km s-1) for QV Nor.

The outburst decay of the low magnetic field magnetar SWIFT J1822.3−1606: phase-resolved analysis and evidence for a variable cyclotron feature

We study the timing and spectral properties of the low-magnetic field, transient magnetar SWIFT J1822.3−1606 as it approached quiescence. We coherently phase-connect the observations over a time-span of ∼500 d since the discovery of SWIFT J1822.3−1606 following the Swift-Burst Alert Telescope (BAT) trigger on 2011 July 14, and carried out a detailed pulse phase spectroscopy along the outburst decay. We follow the spectral evolution of different pulse phase intervals and find a phase and energy-variable spectral feature, which we interpret as proton cyclotron resonant scattering of soft photon from currents circulating in a strong (≳1014 G) small-scale component of the magnetic field near the neutron star surface, superimposed to the much weaker (∼3 × 1013 G) magnetic field. We discuss also the implications of the pulse-resolved spectral analysis for the emission regions on the surface of the cooling magnetar.

Real-Time Gene-Expression Extraction with Fast Classification (FC) Networks

Fast Classification (FC) networks were inspired by a biologically plausible mechanism for short term memory where learning occurs instantaneously. Both weights and the topology for an FC network are mapped directly from the training samples by using a prescriptive training scheme. Only two presentations of the training data are required to train an FC network. Compared with iterative learning algorithms such as Back-propagation (which may require many hundreds of presentations of the training data), the training of FC networks is extremely fast and learning convergence is always guaranteed. Thus FC networks may be suitable for applications where real-time classification is needed. In this paper, the FC networks are applied for the real-time extraction of gene expressions for Chlamydia microarray data. Both the classification performance and learning time of the FC networks are compared with the Multi-Layer Proceptron (MLP) networks and support-vector-machines (SVM) in the same classification task. The FC networks are shown to have extremely fast learning time and comparable classification accuracy.

Fast pyrolysis and nitrogenolysis of biomass and biogenic residues:production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process.

Fast x-ray spectroscopy study of ethene on clean and SO4 precovered Pt{111}

The adsorption and decomposition of ethylene over a Pt{111} single crystalsurface has been investigated by fast x-ray spectroscopy. At 100 K ethene displays precursor-mediated adsorption kinetics, adopting a single environment with a saturation C2H4 coverage of 0.25 ML and binding energy of 283.2 eV. Thermal decomposition proceeds above 240 K via dehydrogenation to ethylidyne with an activation barrier of 57±3 kJ mol−1 and preexponential factor ν=1×1010±0.5 s−1. Site-blocking by preadsorbed SO4 reduces the saturation ethene coverage but induces a new, less reactive π-bonded ethene species centered around 283.9 eV, which in turn decomposes to ethylidyne at 350 K.

Real-time high-resolution heterodyne-based measurements of spectral dynamics in fibre lasers

Conventional tools for measurement of laser spectra (e.g. optical spectrum analysers) capture data averaged over a considerable time period. However, the generation spectrum of many laser types may involve spectral dynamics whose relatively fast time scale is determined by their cavity round trip period, calling for instrumentation featuring both high temporal and spectral resolution. Such real-time spectral characterisation becomes particularly challenging if the laser pulses are long, or they have continuous or quasi-continuous wave radiation components. Here we combine optical heterodyning with a technique of spatiooral intensity measurements that allows the characterisation of such complex sources. Fast, round-trip-resolved spectral dynamics of cavity-based systems in real-time are obtained, with temporal resolution of one cavity round trip and frequency resolution defined by its inverse (85 ns and 24 MHz respectively are demonstrated). We also show how under certain conditions for quasi-continuous wave sources, the spectral resolution could be further increased by a factor of 100 by direct extraction of phase information from the heterodyned dynamics or by using double time scales within the spectrogram approach.

Fast iterative solvers for time-dependent PDE-constrained optimization problems

Otto-von-Guericke-Universität Magdeburg, Fakultät für Mathematik, Kumulative Habilitation, 2016