Analisi e caratterizzazione dei materiali di rinforzo nelle sovrastrutture stradali

Nel presente elaborato è stato studiato l'effetto prodotto dall'inserimento di interstrati di rinforzo tra strati legati di una pavimentazione. Si è realizzato un confronto tra due pavimentazioni, una rinforzata e l'altra di controllo, mediante il software di calcolo OLCRACK, aventi le medesime caratteristiche geometriche e gli stessi materiali. In questo modo è stato possibile osservare l'effetto della griglia di rinforzo nel contrastare e ritardare il fenomeno del reflective cracking. Parallelamente è stata effettuata un'indagine sperimentale in laboratorio su travetti bi-strato rinforzati con due tipologie differenti di griglie. I risultati hanno evidenziato l'importanza del ricoprimento sulla griglia, poiché i travetti più spessi hanno dato una risposta migliore alla vita a fatica. In più è stata osservata l'importanza della resistenza a trazione della griglia nell'incremento dei cicli a rottura dei provini.

To what extent does the Health Professions Admission Test-Ireland predict performance in early undergraduate tests of communication and clinical skills? – An observational cohort study

Background: Internationally, tests of general mental ability are used in the selection of medical students. Examples include the Medical College Admission Test, Undergraduate Medicine and Health Sciences Admission Test and the UK Clinical Aptitude Test. The most widely used measure of their efficacy is predictive validity.A new tool, the Health Professions Admission Test- Ireland (HPAT-Ireland), was introduced in 2009. Traditionally, selection to Irish undergraduate medical schools relied on academic achievement. Since 2009, Irish and EU applicants are selected on a combination of their secondary school academic record (measured predominately by the Leaving Certificate Examination) and HPAT-Ireland score. This is the first study to report on the predictive validity of the HPAT-Ireland for early undergraduate assessments of communication and clinical skills. Method. Students enrolled at two Irish medical schools in 2009 were followed up for two years. Data collected were gender, HPAT-Ireland total and subsection scores; Leaving Certificate Examination plus HPAT-Ireland combined score, Year 1 Objective Structured Clinical Examination (OSCE) scores (Total score, communication and clinical subtest scores), Year 1 Multiple Choice Questions and Year 2 OSCE and subset scores. We report descriptive statistics, Pearson correlation coefficients and Multiple linear regression models. Results: Data were available for 312 students. In Year 1 none of the selection criteria were significantly related to student OSCE performance. The Leaving Certificate Examination and Leaving Certificate plus HPAT-Ireland combined scores correlated with MCQ marks.In Year 2 a series of significant correlations emerged between the HPAT-Ireland and subsections thereof with OSCE Communication Z-scores; OSCE Clinical Z-scores; and Total OSCE Z-scores. However on multiple regression only the relationship between Total OSCE Score and the Total HPAT-Ireland score remained significant; albeit the predictive power was modest. Conclusion: We found that none of our selection criteria strongly predict clinical and communication skills. The HPAT- Ireland appears to measures ability in domains different to those assessed by the Leaving Certificate Examination. While some significant associations did emerge in Year 2 between HPAT Ireland and total OSCE scores further evaluation is required to establish if this pattern continues during the senior years of the medical course.

The Effects of Organic Matter Amendments and Migratory Waterfowl on Greenhouse Gas and Nutrient Dynamics in Managed Coastal Plain Wetlands

Wetland ecosystems provide many valuable ecosystem services, including carbon (C) storage and improvement of water quality. Yet, restored and managed wetlands are not frequently evaluated for their capacity to function in order to deliver on these values. Specific restoration or management practices designed to meet one set of criteria may yield unrecognized biogeochemical costs or co-benefits. The goal of this dissertation is to improve scientific understanding of how wetland restoration practices and waterfowl habitat management affect critical wetland biogeochemical processes related to greenhouse gas emissions and nutrient cycling. I met this goal through field and laboratory research experiments in which I tested for relationships between management factors and the biogeochemical responses of wetland soil, water, plants and trace gas emissions. Specifically, I quantified: (1) the effect of organic matter amendments on the carbon balance of a restored wetland; (2) the effectiveness of two static chamber designs in measuring methane (CH4) emissions from wetlands; (3) the impact of waterfowl herbivory on the oxygen-sensitive processes of methane emission and coupled nitrification-denitrification; and (4) nitrogen (N) exports caused by prescribed draw down of a waterfowl impoundment.

The potency of CH4 emissions from wetlands raises the concern that widespread restoration and/or creation of freshwater wetlands may present a radiative forcing hazard. Yet data on greenhouse gas emissions from restored wetlands are sparse and there has been little investigation into the greenhouse gas effects of amending wetland soils with organic matter, a recent practice used to improve function of mitigation wetlands in the Eastern United States. I measured trace gas emissions across an organic matter gradient at a restored wetland in the coastal plain of Virginia to test the hypothesis that added C substrate would increase the emission of CH4. I found soils heavily loaded with organic matter emitted significantly more carbon dioxide than those that have received little or no organic matter. CH4 emissions from the wetland were low compared to reference wetlands and contrary to my hypothesis, showed no relationship with the loading rate of added organic matter or total soil C. The addition of moderate amounts of organic matter (< 11.2 kg m-2) to the wetland did not greatly increase greenhouse gas emissions, while the addition of high amounts produced additional carbon dioxide, but not CH4.

I found that the static chambers I used for sampling CH4 in wetlands were highly sensitive to soil disturbance. Temporary compression around chambers during sampling inflated the initial chamber CH4 headspace concentration and/or lead to generation of nonlinear, unreliable flux estimates that had to be discarded. I tested an often-used rubber-gasket sealed static chamber against a water-filled-gutter seal chamber I designed that could be set up and sampled from a distance of 2 m with a remote rod sampling system to reduce soil disturbance. Compared to the conventional design, the remotely-sampled static chambers reduced the chance of detecting inflated initial CH4 concentrations from 66 to 6%, and nearly doubled the proportion of robust linear regressions from 45 to 86%. The new system I developed allows for more accurate and reliable CH4 sampling without costly boardwalk construction.

I explored the relationship between CH4 emissions and aquatic herbivores, which are recognized for imposing top-down control on the structure of wetland ecosystems. The biogeochemical consequences of herbivore-driven disruption of plant growth, and in turn, mediated oxygen transport into wetland sediments, were not previously known. Two growing seasons of herbivore exclusion experiments in a major waterfowl overwintering wetland in the Southeastern U.S. demonstrate that waterfowl herbivory had a strong impact on the oxygen-sensitive processes of CH4 emission and nitrification. Denudation by herbivorous birds increased cumulative CH4 flux by 233% (a mean of 63 g CH4 m-2 y-1) and inhibited coupled nitrification-denitrification, as indicated by nitrate availability and emissions of nitrous oxide. The recognition that large populations of aquatic herbivores may influence the capacity for wetlands to emit greenhouse gases and cycle nitrogen is particularly salient in the context of climate change and nutrient pollution mitigation goals. For example, our results suggest that annual emissions of 23 Gg of CH4 y-1 from ~55,000 ha of publicly owned waterfowl impoundments in the Southeastern U.S. could be tripled by overgrazing.

Hydrologically controlled moist-soil impoundment wetlands provide critical habitat for high densities of migratory bird populations, thus their potential to export nitrogen (N) to downstream waters may contribute to the eutrophication of aquatic ecosystems. To investigate the relative importance of N export from these built and managed habitats, I conducted a field study at an impoundment wetland that drains into hypereutrophic Lake Mattamuskeet. I found that prescribed hydrologic drawdowns of the impoundment exported roughly the same amount of N (14 to 22 kg ha-1) as adjacent fertilized agricultural fields (16 to 31 kg ha-1), and contributed approximately one-fifth of total N load (~45 Mg N y-1) to Lake Mattamuskeet. Ironically, the prescribed drawdown regime, designed to maximize waterfowl production in impoundments, may be exacerbating the degradation of habitat quality in the downstream lake. Few studies of wetland N dynamics have targeted impoundments managed to provide wildlife habitat, but a similar phenomenon may occur in some of the 36,000 ha of similarly-managed moist-soil impoundments on National Wildlife Refuges in the southeastern U.S. I suggest early drawdown as a potential method to mitigate impoundment N pollution and estimate it could reduce N export from our study impoundment by more than 70%.

In this dissertation research I found direct relationships between wetland restoration and impoundment management practices, and biogeochemical responses of greenhouse gas emission and nutrient cycling. Elevated soil C at a restored wetland increased CO2 losses even ten years after the organic matter was originally added and intensive herbivory impact on emergent aquatic vegetation resulted in a ~230% increase in CH4 emissions and impaired N cycling and removal. These findings have important implications for the basic understanding of the biogeochemical functioning of wetlands and practical importance for wetland restoration and impoundment management in the face of pressure to mitigate the environmental challenges of global warming and aquatic eutrophication.

Analysis of Cosmogenic Impurities in Tellurium and Development of Tellurium Loading for the SNO+ Experiment

For the SNO+ neutrinoless double beta decay search, various backgrounds, ranging from impurities present naturally to those produced cosmogenically, must be understood and reduced. Cosmogenic backgrounds are particularly difficult to reduce as they are continually regenerated while exposed to high energy cosmic rays. To reduce these cosmogenics as much as possible the tellurium used for the neutrinoless double beta decay search will be purified underground. An analysis of the purification factors achievable for insoluble cosmogenic impurities found a reduction factor of $>$20.4 at 50\% C.L.. During the purification process the tellurium will come into contact with ultra pure water and nitric acid. These liquids both carry some cosmogenic impurities with them that could be potentially transferred to the tellurium. A conservative limit is set at $<$18 events in the SNO+ region of interest (ROI) per year as a result of contaminants from these liquids. In addition to cosmogenics brought underground, muons can produce radioactive isotopes while the tellurium is stored underground. A study on the rate at which muons produce these backgrounds finds an additional 1 event per year. In order to load the tellurium into the detector, it will be combined with 1,2-butanediol to form an organometallic complex. The complex was found to have minimal effect on the SNO+ acrylic vessel for 154 years.

Basalt Fibre Reinforced Polymer Strengthening of Normal Strength Reinforced Concrete Floor Slabs Subject to Arching Effects

With ever increasing demands to strengthen existing reinforced concrete structures to facilitate higher loading due to change of use and to extend service lifetime, the use of fibre reinforced polymers (FRPs) in structural retrofitting offers an opportunity to achieve these aims. To date, most research in this area has focussed on the use of glass fibre reinforced polymer (GFRP) and carbon fibre reinforced polymer (CFRP), with relatively little on the use of basalt fibre reinforced polymer (BFRP) as a suitable strengthening material. In addition, most previous research has been carried out using simply supported elements, which have not considered the beneficial influence of in-plane lateral restraint, as experienced within a framed building structure. Furthermore, by installing FRPs using the near surface mounted (NSM) technique, disturbance to the existing structure can be minimised.
This paper outlines BFRP NSM strengthening of one third scale laterally restrained floor slabs which reflect the inherent insitu compressive membrane action (CMA) in such slabs. The span-to-depth ratios of the test slabs were 20 and 15 and all were constructed with normal strength concrete (~40N/mm2) and 0.15% steel reinforcement. 0.10% BFRP was used in the retrofitted samples, which were compared with unretrofitted control samples. In addition, the bond strength of BFRP bars bonded into concrete was investigated over a range of bond lengths with two different adhesive thicknesses. This involved using an articulated beam arrangement in order to establish optimum bond characteristics for use in strengthening slab samples.

Laboratory performance evaluation of CIR-emulsion and its comparison against CIR-foam test results from Phase III, TR-578

Currently, no standard mix design procedure is available for CIR-emulsion in Iowa. The CIR-foam mix design process developed during the previous phase is applied for CIR-emulsion mixtures with varying emulsified asphalt contents. Dynamic modulus test, dynamic creep test, static creep test and raveling test were conducted to evaluate the short- and long-term performance of CIR-emulsion mixtures at various testing temperatures and loading conditions. A potential benefit of this research is a better understanding of CIR-emulsion material properties in comparison with those of CIR-foam material that would allow for the selection of the most appropriate CIR technology and the type and amount of the optimum stabilization material. Dynamic modulus, flow number and flow time of CIR-emulsion mixtures using CSS-1h were generally higher than those of HFMS-2p. Flow number and flow time of CIR-emulsion using RAP materials from Story County was higher than those from Clayton County. Flow number and flow time of CIR-emulsion with 0.5% emulsified asphalt was higher than CIR-emulsion with 1.0% or 1.5%. Raveling loss of CIR-emulsion with 1.5% emulsified was significantly less than those with 0.5% and 1.0%. Test results in terms of dynamic modulus, flow number, flow time and raveling loss of CIR-foam mixtures are generally better than those of CIR-emulsion mixtures. Given the limited RAP sources used for this study, it is recommended that the CIR-emulsion mix design procedure should be validated against several RAP sources and emulsion types.

Collaborative Filtering with Data Classification : A Combined Approach to Hotel Recommendation Systems

Recommendation systems aim to help users make decisions more efficiently. The most widely used method in recommendation systems is collaborative filtering, of which, a critical step is to analyze a user's preferences and make recommendations of products or services based on similarity analysis with other users' ratings. However, collaborative filtering is less usable for recommendation facing the "cold start" problem, i.e. few comments being given to products or services. To tackle this problem, we propose an improved method that combines collaborative filtering and data classification. We use hotel recommendation data to test the proposed method. The accuracy of the recommendation is determined by the rankings. Evaluations regarding the accuracies of Top-3 and Top-10 recommendation lists using the 10-fold cross-validation method and ROC curves are conducted. The results show that the Top-3 hotel recommendation list proposed by the combined method has the superiority of the recommendation performance than the Top-10 list under the cold start condition in most of the times.

Behavior of Granular Materials Under Triaxial Compression with Pulsating Deviator Stress, HR-131, Special Report

Behavior of granular material subjected to repeated load triaxial compression tests is characterized by a model based on rate process theory. Starting with the Arrhenius equation from chemical kinetics, the relationship of temperature, shear stress, normal stress and volume change to deformation rate is developed. The proposed model equation includes these factors as a product of exponential terms. An empirical relationship between deformation and the cube root of the number of stress applications at constant temperature and normal stress is combined with the rate equation to yield an integrated relationship of temperature, deviator stress, confining pressure and number of deviator stress applications to axial strain. The experimental program consists of 64 repeated load triaxial compression tests, 52 on untreated crushed stone and 12 on the same crushed stone material treated with 4% asphalt cement. Results were analyzed with multiple linear regression techniques and show substantial agreement with the model equations. Experimental results fit the rate equation somewhat better than the integrated equation when all variable quantities are considered. The coefficient of shear temperature gives the activation enthalpy, which is about 4.7 kilocalories/mole for untreated material and 39.4 kilocalories/mole for asphalt-treated material. This indicates the activation enthalpy is about that of the pore fluid. The proportionality coefficient of deviator stress may be used to measure flow unit volume. The volumes thus determined for untreated and asphalt-treated material are not substantially different. This may be coincidental since comparison with flow unit volumes reported by others indicates flow unit volume is related to gradation of untreated material. The flow unit volume of asphalt-treated material may relate to asphalt cement content. The proposed model equations provide a more rational basis for further studies of factors affecting deformation of granular materials under stress similar to that in pavement subjected to transient traffic loads.

Characterization of the glial scar tissue in a murine model of spinal cord compression, with focus on hyaluronan

Spinal cord injury (SCI) is a devastating neurological disorder that affects thousands of people each year. Although in recent decades significant progress has been made in relation to understanding the molecular and cellular events underlying the nervous damage, spinal cord injury is still a highly disabling condition for which there is no curative therapy. People affected by spinal cord injuries manifested dysfunction or loss, temporary or permanent, of motor, sensory and / or autonomic functions depending on the spinal lesion damaged. Currently, the incidence rate of this type of injury is approximately 15-40 cases per million people worldwide. At the origin of these lesions are: road accidents, falls, interpersonal violence and the practice of sports. In this work we placed the hypothesis that HA is one of the component of the scar tissue formed after a compressive SCI, that it is likely synthetised by the perilesional glial cells and that it might support the permeation of the glial scar during the late phase of SCI. Nowadays, much focus is drawn on the recovery of CNS function, made impossible after SCI due to the high content of sulfated proteoglycans in the extracellular matrix. Counterbalancing the ratio between these proteoglycans and hyaluronic acid could be one of the experimental therapy to re-permeate the glial scar tissue formed after SCI, making possible axonal regrowth and functional recovery. Therefore, we established a model of spinal cord compression in mice and studied the glial scar tissue, particularly through the characterization of the expression of enzymes related to the metabolism of HA and the subsequent concentration thereof at different distances of the lesion epicenter. Our results show that the lesion induced in mice shows results similar to those produced in human lesions, in terms of histologic similarities and behavioral results. but these animals demonstrate an impressive spontaneous reorganization mechanism of the spinal cord tissue that occurs after injury and allows for partial recovery of the functions of the CNS. As regards the study of the glial scar, changes were recorded at the level of mRNA expression of enzymes metabolizing HA i.e., after injury there was a decreased expression of HA synthases 1-2 (HAS 1-2) and an increase of the expression HAS3 synthase mRNA, as well as the enzymes responsible for the HA catabolism, HYAL 1-2. But the amount of HA measured through the ELISA test was found unchanged after injury, it is not possible to explain this fact only with the change of expression of enzymes. At two weeks and in response to SCI, we found synthesized HA by reactive astrocytes and probably by others like microglial cells as it was advanced by the HA/GFAP+ and HA/IBA1+ cells co-location.

CHARACTERIZATION OF TOBACCO MOSAIC VIRUS DIRECTED REPROGRAMMING OF PHLOEM GENE EXPRESSION TO PROMOTE VIRAL PHLOEM LOADING AND SYSTMEIC MOVEMENT

Vascular phloem loading has long been recognized as an essential step in the establishment of a systemic virus infection. Yet little is known about this process and the mechanisms that control it. In this study, an interaction between the replication protein of Tobacco mosaic virus (TMV) and phloem specific auxin/indole acetic acid (Aux/IAA) transcriptional regulators was found to modulate virus phloem loading. Promoter expression studies show TMV 126/183 kDa interacting Aux/IAAs predominantly express and accumulate within the nuclei of phloem companion cells (CC). Furthermore, CC Aux/IAA nuclear localization is disrupted upon infection with an interacting virus but not during infection with a non-interacting virus. In situ analysis of virus spread shows the inability of TMV variants to disrupt Aux/IAA CC nuclear localization correlates with a reduced ability to load into the vascular tissue. Subsequent systemic movement assays also demonstrate that a virus capable of disrupting Aux/IAA localization is significantly more competitive at systemic movement than a non-interacting virus. Similarly, CC expression and over-accumulation of a degradation-resistant-interacting Aux/IAA protein was found to selectively inhibit TMV accumulation and phloem loading. Transcriptional expression studies demonstrate a role for interacting Aux/IAA proteins in the regulation of salicylic acid and jasmonic acid dependent host defense responses as well as virus specific movement factors including pectin methylesterase that are involved in regulating plasmodesmata size exclusion limits and promoting virus cell-to-cell movement. Further characterization of the phloem environment was done using two phloem specific promoters (pSUC2 and pSULTR2;2) to generate epitope-tagged polysomal-RNA complexes. Immuno-purification using the epitope tag allowed us to obtain mRNAs bound to polysomes (the translatome) specifically in phloem tissue. We found the phloem translatome is uniquely altered during TMV infection with 90% and 88% of genes down regulated in the pSUC2 and pSULTR2;2 phloem translatomes, compared to 31% of genes down regulated in the whole plant p35S translatome. Transcripts down regulated in phloem include genes involved in callose deposition at plasmodesmata, host defense responses, and RNA silencing. Combined, these findings indicate TMV reprograms gene expression within the vascular phloem as a means to enhance phloem loading and systemic spread.

Small strain elastic behaviour of unsaturated soil investigated by bender/extender element testing

The aim of this project was to investigate very small strain elastic behaviour of soils under unsaturated conditions, using bender/extender element (BEE) testing. The behaviour of soils at very small strains has been widely studied under saturated conditions, whereas much less work has been performed on very small strain behaviour under unsaturated conditions. A suction-controlled double wall triaxial apparatus for unsaturated soil testing was modified to incorporate three pairs of BEEs transmitting both shear and compression waves with vertical and horizontal directions of wave transmission and wave polarisation. Various different techniques for measuring wave travel time were investigated in both the time domain and the frequency domain and it was concluded that, at least for the current experimental testing programme, peak-to-first-peak in the time domain was the most reliable technique for determining wave travel time. An experimental test programme was performed on samples of compacted speswhite kaolin clay. Two different forms of compaction were employed (i.e. isotropic and anisotropic). Compacted kaolin soil samples were subjected to constant suction loading and unloading stages at three different values of suction, covering both unsaturated conditions (s= 50kPa and s= 300kPa) and saturated conditions (s=0). Loading and unloading stages were performed at three different values of stress ratio (η=0, η=1 and η=-1 ). In some tests a wetting-drying cycle was performed before or within the loading stage, with the wetting-drying cycles including both wetting-induced swelling and wetting-induced collapse compression. BEE tests were performed at regular intervals throughout all test stages, to measure shear wave velocity Vs and compression wave velocity Vp and hence to determine values of shear modulus G and constrained modulus M. The experimental test programme was designed to investigate how very small strain shear modulus G and constrained modulus M varied with unsaturated state variables, including how anisotropy of these parameters developed either with stress state (stress-induced anisotropy) or with previous straining (strain-induced anisotropy). A new expression has been proposed for the very small strain shear modulus G of an isotropic soil under saturated and unsaturated conditions. This expression relates the variation of G to only mean Bishop’s stress p* and specific volume v, and it converges to a well-established expression for saturated soils as degree of saturation approaches 1. The proposed expression for G is able to predict the variation of G under saturated and unsaturated conditions at least as well as existing expressions from the literature and it is considerably simpler (employing fewer state variables and fewer soil constants). In addition, unlike existing expressions from the literature, the values of soil constants in the proposed new expression can be determined from a saturated test. It appeared that, in the current project at least, any strain-induced anisotropy of very small strain elastic behaviour was relatively modest, with the possible exception of loading in triaxial extension. It was therefore difficult to draw any firm conclusion about evolution of strain-induced anisotropy and whether it depended upon the same aspects of soil fabric as evolution of anisotropy of large strain plastic behaviour. Stress-induced anisotropy of very small strain elastic behaviour was apparent in the experimental test programme. An attempt was made to extend the proposed expression for G to include the effect of stress-induced anisotropy. Interpretation of the experimental results indicated that the value of shear modulus was affected by the values of all three principal Bishop’s stresses (in the direction of wave transmission, the direction of wave polarisation and the third mutually perpendicular direction). However, prediction of stress-induced anisotropy was only partially successful, and it was concluded that the effect of Lode angle was also significant.

3D Porous Architecture of Stacks of β-TCP Granules Compared with That of Trabecular Bone: A microCT, Vector Analysis, and Compression Study

International audience

Quantitative phase Analisis: A comparative study of Mo and Cu strictly monochromatic radiations

A comparison of the Rietveld quantitative phase analyses (RQPA) obtained using Cu-Kα1, Mo-Kα1, and synchrotron strictly monochromatic radiations is presented. The main aim is to test a simple hypothesis: high energy Mo-radiation, combined with high resolution laboratory X-ray powder diffraction optics, could yield more accurate RQPA, for challenging samples, than well-established Cu-radiation procedure(s). In order to do so, three set of mixtures with increasing amounts of a given phase (spiking-method) were prepared and the corresponding RQPA results have been evaluated. Firstly, a series of crystalline inorganic phase mixtures with increasing amounts of an analyte was studied in order to determine if Mo-Kα1 methodology is as robust as the well-established Cu-Kα1 one. Secondly, a series of crystalline organic phase mixtures with increasing amounts of an organic compound was analyzed. This type of mixture can result in transparency problems in reflection and inhomogeneous loading in narrow capillaries for transmission studies. Finally, a third series with variable amorphous content was studied. Limit of detection in Cu-patterns, ~0.2 wt%, are slightly lower than those derived from Mo-patterns, ~0.3 wt%, for similar recording times and limit of quantification for a well crystallized inorganic phase using laboratory powder diffraction was established ~0.10 wt%. However, the accuracy was comprised as relative errors were ~100%. Contents higher than 1.0 wt% yielded analyses with relative errors lower than 20%. From the obtained results it is inferred that RQPA from Mo-Kα1 radiation have slightly better accuracies than those obtained from Cu-Kα1. This behavior has been established with the calibration graphics obtained through the spiking method and also from Kullback-Leibler distance statistic studies. We explain this outcome, in spite of the lower diffraction power for Mo-radiation (compared to Cu-radiation), due to the larger volume tested with Mo, also because higher energy minimize pattern systematic errors and the microabsorption effect.

The use of mo and cu monochromatic radiations for quantitative phase analysis: study of the accuracy

Cement hydration is a very complex process in which crystalline phases are dissolving in water and after supersaturation hydrated crystalline and amorphous phases precipitate. Great efforts are being made to develop analytical tools to accurately quantify these processes and X-ray Powder Diffraction (XRPD) combined with Rietveld methodology is a suitable tool to quantify these complex mixtures and their time evolutions. However, some problems/drawbacks should be overcome to fully apply it to cement pastes characterization in order to get accurate phase analyses. In order to tackle this issue, a comparison of the Rietveld quantitative phase analyses (RQPA) obtained using Cu-Kα1, Mo-Kα1, and synchrotron strictly monochromatic radiations of three set of mixtures with increasing amounts of a given phase (spiking-method) is presented. The main aim is to test a simple hypothesis: high energy Mo-radiation, combined with high resolution laboratory X-ray powder diffraction optics, could yield more accurate RQPA, for challenging samples, than well-established Cu-radiation procedure(s). Firstly, a series of crystalline inorganic phase mixtures with increasing amounts of an analyte was studied in order to determine if Mo-Kα1 methodology is as robust as the well-established Cu-Kα1 one. Secondly, a series of crystalline organic phase mixtures with increasing amounts of an organic compound was analyzed. This type of mixture can result in transparency problems in reflection and inhomogeneous loading in narrow capillaries for transmission studies. Finally, a third series with variable amorphous content was studied. Limit of detection in Cu-patterns, ~0.2 wt%, are slightly lower than those derived from Mo-patterns, ~0.3 wt%, for similar recording times and limit of quantification for a well crystallized inorganic phase using laboratory powder diffraction was established ~0.10 wt%. From the obtained results it is inferred that RQPA from Mo-Kα1 radiation have slightly better accuracies than those obtained from Cu-Kα1. The results obtained in the previous comparison have been taken into account to obtain accurate RQPA, including the amorphous component with internal standard methodology, of hydrating cement pastes. The final goal of this second study was understanding the early-stage hydration mechanisms of a variety of cementing systems (Ordinary Portland Cement or Belite Alite Ye’elimite cement) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, X-ray powder diffraction data were taken in-situ with the humidity chamber coupled to the Mo-Kα1 powder diffractometer. Some results of this ongoing investigation will be reported and discussed.

Accessori per sistemi in cavo nella trasmissione dell'energia elettrica in HVDC: definizione di modelli fisici per la caratterizzazione di materiali isolanti, semiconduttivi e varioresistivi

Lo studio intrapreso si è posto come obiettivo la caratterizzazione dal punto di vista elettrico dei materiali coinvolti nella realizzazione di accessori per applicazioni in HVDC, in particolare mescole isolanti, semiconduttive e varioresistive. La necessità di un lavoro di questo tipo viene giustificata dalla costante espansione dei sistemi in DC nella trasmissione dell’energia elettrica, i quali presentano caratteristiche fisiche che si differenziano sensibilmente da quelle tipiche dei tradizionali sistemi in AC, dunque richiedono componenti e materiali opportunamente progettati per garantire condizioni di servizio sicure e affidabili. L’obiettivo della trattazione consiste nello studio di analogie e differenze tra le proprietà elettriche fornite da prove su diverse configurazioni di provini, nella fattispecie di tipo piano e cilindrico cavo. In primo luogo si studiano i provini di tipo piano al fine di ricavare informazioni basilari sul materiale e sulla mescola che lo costituisce e di prendere decisioni relative al proseguimento dei test. Dopo aver effettuato un sufficiente numero di test su varie tipologie di provini piani e aver riconosciuto le mescole più performanti dal punto di vista elettrico, meccanico e termico, si procede alla realizzazione di provini cilindrici stampati, su cui si intraprendono le medesime misure effettuate per la configurazione piana. Questa seconda fase di caratterizzazione è fondamentale, in quanto consente di verificare che le proprietà già studiate su piastra si conservino in una geometria molto più simile a quella assunta dal prodotto finale evitando di sostenere costi onerosi per la produzione di un accessorio full-size. Il lavoro è stato svolto nel laboratorio elettrico di alta tensione della divisione R&D del gruppo Prysmian di Milano, leader mondiale nella produzione di sistemi in cavo per alte e altissime tensioni.