Physiological consequences of early-life insult

The most commonly observed severe lung injuries in early life are the respiratory distress syndrome in premature infants and the acute respiratory distress syndrome in children. Both diseases are characterised by alveolar instability, fluid filled airspace and some degree of airway obstruction. In the acute phase, collapsed alveoli can be reopened with positive end-expiratory pressure and lung recruitment. New insight into the physiology of lung recruitment suggests that the shape of the pressure–volume curve is defined by the change in rate of alveolar opening and closing. Reduced lung volumes and severe ventilation maldistribution are found in the acute phase but may persist during childhood. Any severe lung injury in this early phase of life can cause significant structural and functional damage to the developing lung. Follow-up studies of children with chronic lung disease have shown that the functional abnormalities will improve but may still be present in later childhood.

The effect of caudal block on functional residual capacity and ventilation homogeneity in healthy children

Caudal block results in a motor blockade that can reduce abdominal wall tension. This could interact with the balance between chest wall and lung recoil pressure and tension of the diaphragm, which determines the static resting volume of the lung. On this rationale, we hypothesised that caudal block causes an increase in functional residual capacity and ventilation distribution in anaesthetised children. Fifty-two healthy children (15-30 kg, 3-8 years of age) undergoing elective surgery with general anaesthesia and caudal block were studied and randomly allocated to two groups: caudal block or control. Following induction of anaesthesia, the first measurement was obtained in the supine position (baseline). All children were then turned to the left lateral position and patients in the caudal block group received a caudal block with bupivacaine. No intervention took place in the control group. After 15 nun in the supine position, the second assessment was performed. Functional residual capacity and parameters of ventilation distribution were calculated by a blinded reviewer. Functional residual capacity was similar at baseline in both groups. In the caudal block group, the capacity increased significantly (p < 0.0001) following caudal block, while in the control group, it remained unchanged. In both groups, parameters of ventilation distribution were consistent with the changes in functional residual capacity. Caudal block resulted in a significant increase in functional residual capacity and improvement in ventilation homogeneity in comparison with the control group. This indicates that caudal block might have a beneficial effect on gas exchange in anaesthetised, spontaneously breathing preschool-aged children with healthy lungs.

Hydrostatic pressure sensing using a polymer optical fibre Bragg gratings

The sensitivity of a fibre Bragg grating (FBG) sensor fabricated in polymer optical fibre (POF) to hydrostatic pressure was investigated for the first time. In this initial investigative work a reflected Bragg response of a FBG fabricated in multimode microstructured POF (MMmPOF) was monitored, whilst the hydrostatic pressure was increased up to 10MPa. Positive sensitivities were observed, meaning a positive wavelength shift to increasing pressure, as opposed to negative sensitivities monitored when using a FBG sensor fabricated in silica optical fibre. The FBG sensors fabricated in the MMmPOF gave fractional changes in wavelength and hence sensitivities of at least 64.05×10-6/MPa, which is some 25 times larger than the -2.50×10-6/MPa sensitivity of a FBG sensor fabricated in silica optical fibre that was measured in this work. Furthermore this work highlighted a decrease in sensitivity of the FBG sensor fabricated in the MMmPOF by some 50% by sealing the holes of the mPOF at the tip of the fibre with an adhesive. This offers the potential to tailor the response of the sensor to hydrostatic pressure.

Hydrostatic pressure sensing using a polymer optical fibre Bragg gratings

The sensitivity of a fibre Bragg grating (FBG) sensor fabricated in polymer optical fibre (POF) to hydrostatic pressure was investigated for the first time. In this initial investigative work a reflected Bragg response of a FBG fabricated in multimode microstructured POF (MMmPOF) was monitored, whilst the hydrostatic pressure was increased up to 10MPa. Positive sensitivities were observed, meaning a positive wavelength shift to increasing pressure, as opposed to negative sensitivities monitored when using a FBG sensor fabricated in silica optical fibre. The FBG sensors fabricated in the MMmPOF gave fractional changes in wavelength and hence sensitivities of at least 64.05×10-6/MPa, which is some 25 times larger than the -2.50×10-6/MPa sensitivity of a FBG sensor fabricated in silica optical fibre that was measured in this work. Furthermore this work highlighted a decrease in sensitivity of the FBG sensor fabricated in the MMmPOF by some 50% by sealing the holes of the mPOF at the tip of the fibre with an adhesive. This offers the potential to tailor the response of the sensor to hydrostatic pressure.

High pressure and low temperature study of ammonia borane and lithium amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the "hydrogen economy" faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH 3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. ^ Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. ^ Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn2 1 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.^

Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

Physical Insights, Steady Aerodynamic Effects, and a Design Tool for Low-Pressure Turbine Flutter

The successful, efficient, and safe turbine design requires a thorough understanding of the underlying physical phenomena. This research investigates the physical understanding and parameters highly correlated to flutter, an aeroelastic instability prevalent among low pressure turbine (LPT) blades in both aircraft engines and power turbines. The modern way of determining whether a certain cascade of LPT blades is susceptible to flutter is through time-expensive computational fluid dynamics (CFD) codes. These codes converge to solution satisfying the Eulerian conservation equations subject to the boundary conditions of a nodal domain consisting fluid and solid wall particles. Most detailed CFD codes are accompanied by cryptic turbulence models, meticulous grid constructions, and elegant boundary condition enforcements all with one goal in mind: determine the sign (and therefore stability) of the aerodynamic damping. The main question being asked by the aeroelastician, ``is it positive or negative?'' This type of thought-process eventually gives rise to a black-box effect, leaving physical understanding behind. Therefore, the first part of this research aims to understand and reveal the physics behind LPT flutter in addition to several related topics including acoustic resonance effects. A percentage of this initial numerical investigation is completed using an influence coefficient approach to study the variation the work-per-cycle contributions of neighboring cascade blades to a reference airfoil. The second part of this research introduces new discoveries regarding the relationship between steady aerodynamic loading and negative aerodynamic damping. Using validated CFD codes as computational wind tunnels, a multitude of low-pressure turbine flutter parameters, such as reduced frequency, mode shape, and interblade phase angle, will be scrutinized across various airfoil geometries and steady operating conditions to reach new design guidelines regarding the influence of steady aerodynamic loading and LPT flutter. Many pressing topics influencing LPT flutter including shocks, their nonlinearity, and three-dimensionality are also addressed along the way. The work is concluded by introducing a useful preliminary design tool that can estimate within seconds the entire aerodynamic damping versus nodal diameter curve for a given three-dimensional cascade.

High-pressure experiments on a natural olivine gabbro from ODP Hole 176-735B

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4-9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ~10* greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts.Yaxley-Sobolev

Understanding Adolescents’ Positive and Negative Developmental Experiences in Sport

The purpose of this study was to gain understanding of adolescents’ positive and negative developmental experiences in sport. Twenty-two purposefully sampled adolescent competitive swimmers participated in a semistructured qualitative interview. Content analysis led to the organization of meaning units into themes and categories (Patton, 2002). Athletes suggested their sport involvement facilitated many positive developmental experiences (i.e., related to challenge, meaningful adult and peer relationships, a sense of community, and other life experiences) and some negative developmental experiences (i.e., related to poor coach relationships, negative peer influences, parent pressure, and the challenging psychological environment of competitive sport). Findings underline the important roles of sport programmers, clubs, coaches, and parents in facilitating youths’ positive developmental experiences in sport, while highlighting numerous important directions for future research. Implications for coach training and practice are outlined.

Epidemiology and genetic architecture of blood pressure: a family based study of Generation Scotland

Hypertension is a major risk factor for cardiovascular disease and mortality, and a growing global public health concern, with up to one-third of the world’s population affected. Despite the vast amount of evidence for the benefits of blood pressure (BP) lowering accumulated to date, elevated BP is still the leading risk factor for disease and disability worldwide. It is well established that hypertension and BP are common complex traits, where multiple genetic and environmental factors contribute to BP variation. Furthermore, family and twin studies confirmed the genetic component of BP, with a heritability estimate in the range of 30-50%. Contemporary genomic tools enabling the genotyping of millions of genetic variants across the human genome in an efficient, reliable, and cost-effective manner, has transformed hypertension genetics research. This is accompanied by the presence of international consortia that have offered unprecedentedly large sample sizes for genome-wide association studies (GWASs). While GWAS for hypertension and BP have identified more than 60 loci, variants in these loci are associated with modest effects on BP and in aggregate can explain less than 3% of the variance in BP. The aims of this thesis are to study the genetic and environmental factors that influence BP and hypertension traits in the Scottish population, by performing several genetic epidemiological analyses. In the first part of this thesis, it aims to study the burden of hypertension in the Scottish population, along with assessing the familial aggregation and heritialbity of BP and hypertension traits. In the second part, it aims to validate the association of common SNPs reported in the large GWAS and to estimate the variance explained by these variants. In this thesis, comprehensive genetic epidemiology analyses were performed on Generation Scotland: Scottish Family Health Study (GS:SFHS), one of the largest population-based family design studies. The availability of clinical, biological samples, self-reported information, and medical records for study participants has allowed several assessments to be performed to evaluate factors that influence BP variation in the Scottish population. Of the 20,753 subjects genotyped in the study, a total of 18,470 individuals (grouped into 7,025 extended families) passed the stringent quality control (QC) criteria and were available for all subsequent analysis. Based on the BP-lowering treatment exposure sources, subjects were further classified into two groups. First, subjects with both a self-reported medications (SRMs) history and electronic-prescription records (EPRs; n =12,347); second, all the subjects with at least one medication history source (n =18,470). In the first group, the analysis showed a good concordance between SRMs and EPRs (kappa =71%), indicating that SRMs can be used as a surrogate to assess the exposure to BP-lowering medication in GS:SFHS participants. Although both sources suffer from some limitations, SRMs can be considered the best available source to estimate the drug exposure history in those without EPRs. The prevalence of hypertension was 40.8% with higher prevalence in men (46.3%) compared to women (35.8%). The prevalence of awareness, treatment and controlled hypertension as defined by the study definition were 25.3%, 31.2%, and 54.3%, respectively. These findings are lower than similar reported studies in other populations, with the exception of controlled hypertension prevalence, which can be considered better than other populations. Odds of hypertension were higher in men, obese or overweight individuals, people with a parental history of hypertension, and those living in the most deprived area of Scotland. On the other hand, deprivation was associated with higher odds of treatment, awareness and controlled hypertension, suggesting that people living in the most deprived area may have been receiving better quality of care, or have higher comorbidity levels requiring greater engagement with doctors. These findings highlight the need for further work to improve hypertension management in Scotland. The family design of GS:SFHS has allowed family-based analysis to be performed to assess the familial aggregation and heritability of BP and hypertension traits. The familial correlation of BP traits ranged from 0.07 to 0.20, and from 0.18 to 0.34 for parent-offspring pairs and sibling pairs, respectively. A higher correlation of BP traits was observed among first-degree relatives than other types of relative pairs. A variance-component model that was adjusted for sex, body mass index (BMI), age, and age-squared was used to estimate heritability of BP traits, which ranged from 24% to 32% with pulse pressure (PP) having the lowest estimates. The genetic correlation between BP traits showed a high correlation between systolic (SBP), diastolic (DBP) and mean arterial pressure (MAP) (G: 81% to 94%), but lower correlations with PP (G: 22% to 78%). The sibling recurrence risk ratio (λS) for hypertension and treatment were calculated as 1.60 and 2.04 respectively. These findings confirm the genetic components of BP traits in GS:SFHS, and justify further work to investigate genetic determinants of BP. Genetic variants reported in the recent large GWAS of BP traits were selected for genotyping in GS:SFHS using a custom designed TaqMan® OpenArray®. The genotyping plate included 44 single nucleotide polymorphisms (SNPs) that have been previously reported to be associated with BP or hypertension at genome-wide significance level. A linear mixed model that is adjusted for age, age-squared, sex, and BMI was used to test for the association between the genetic variants and BP traits. Of the 43 variants that passed the QC, 11 variants showed statistically significant association with at least one BP trait. The phenotypic variance explained by these variant for the four BP traits were 1.4%, 1.5%, 1.6%, and 0.8% for SBP, DBP, MAP, and PP, respectively. The association of genetic risk score (GRS) that were constructed from selected variants has showed a positive association with BP level and hypertension prevalence, with an average effect of one mmHg increase with each 0.80 unit increases in the GRS across the different BP traits. The impact of BP-lowering medication on the genetic association study for BP traits has been established, with typical practice of adding a fixed value (i.e. 15/10 mmHg) to the measured BP values to adjust for BP treatment. Using the subset of participants with the two treatment exposure sources (i.e. SRMs and EPRs), the influence of using either source to justify the addition of fixed values in SNP association signal was analysed. BP phenotypes derived from EPRs were considered the true phenotypes, and those derived from SRMs were considered less accurate, with some phenotypic noise. Comparing SNPs association signals between the four BP traits in the two model derived from the different adjustments showed that MAP was the least impacted by the phenotypic noise. This was suggested by identifying the same overlapped significant SNPs for the two models in the case of MAP, while other BP traits had some discrepancy between the two sources

Pressure ulcer management in Oman: nurses’ knowledge and views

Background: Pressure ulcers (PrUs) have a significant impact on health system expenditure and patient’s quality of life. It is a global problem. Many studies were undertaken in regard to PrU prevention and management. In Oman, no studies have been conducted to investigate nurses’ knowledge on prevention and management of PrUs. The purpose of this descriptive sequential explanatory mixed-method study was to explore the nurses’ level of knowledge in relation to prevention and management of PrUs in Oman. Methods: A mixed method design was used and the study was conducted over two Phases. In Phase I, a questionnaire was developed to explore nurses’ knowledge on PrU, policy, and resources. The main section of the questionnaire was the Pieper-Zulkowski Pressure Ulcer knowledge test (PZ-PUKT) which tests the knowledge on PrU. Another two sections were developed including questions about wound policy and resources available for PrU prevention and management in Oman. The questionnaire was distributed to nurses who were working in surgical, medical, orthopaedic, CCU, and ICU wards/units in seven hospitals. In Phase II study, semi-structured qualitative interviews were conducted with 16 of the questionnaire respondents. Interviews took approximately 30 minutes, were recorded and transcribed verbatim. Qualitative data were analysed using the Knowledge, Attitudes and Practice (KAP) model as the a priori framework. Results: In Phase I, 478 questionnaires were analysed. The knowledge test results showed the overall mean percent score for correctly answered questions was 51% suggesting a low level of knowledge. There was a significant relationship between nurses’ knowledge and age (P=0.001) and between knowledge and years of experience (P=0.001) with knowledge increasing with age and years of experience. In Phase II, four themes were identified from the interviews: knowledge, attitude, and practice (framework themes) and perception of role. Findings indicated positive and negative attitudes towards the care of PrUs. Some nurses stated feeling rewarded when they see wounds improving while others said they could not work with patients independently because they lacked the knowledge and the skills needed. There was variation in the management of PrU between hospitals. Both studies indicated that the wound management policy did not include enough information to guide nurses. Conclusion: Overall the nurses’ level of knowledge on PrU was relatively low. Most nurses were not familiar with wound management policy or different PrU prevention and management strategies. Nurses are aware of the risk of PrUs and try their best to manage them with the available resources however more training is required.

Characterization of patients undergoing noninvasive ventilation admitted in unit intermediate care

Non-invasive ventilation (NIV) is the application of a ventilatory support without resorting to invasive methods. Today it’s considered a credible therapeutic option, with enough scientiic evidence to support its application in various situations and clinical settings related to the treatment of acute respiratory disease, as well as chronic respiratory disease. Objectives: Characterize patients undergoing NIV admitted in Unit Intermediate Care (ICU) in the period from October 1st 2015 to June 30th 2016. Methods: Prospective study conducted in ICU between October 2015 and June 2016. In this study were included all patients hospitalized in this unit (ICU) and in that time period a sample of 57 participants was obtained. As data collection instruments we used a questionnaire for sociodemographic and clinical data and the Braden scale. Results: Participants were mostly male 38 (66.7%), the average age 69.5 ± 11.3 years, ranging between 43 and 92 years. They weighed on average 76.6 kg (52 and 150), with an average body mass index of 28.5 kg/m2 (20 to 58.5). With skin intact 28 (49.1%) with abnormal perfusion 12 (21.1%), with altered sensitivity 11 (19.3%) and a high risk of ulcer on the scale of Braden 37 (65%). The admission diagnosis was respiratory failure 33 (57.3%) and had different backgrounds. We used reused mask 53 (93.0%), the average time of NIV was 7.1 days (1-28), 4.8 days of hospitalization (1-18) and an average of 7.8 IPAP pressure. 11 (19.3%) of the participants developed face ulcer pressure.Conclusions: The NIV is used in patients with advanced age, obesity, respiratory failure and high risk of face ulcer development.

L'activité tonique diaphragmatique chez les enfants avec et sans support respiratoire

Introduction : Les nourrissons, vu la grande compliance de leur cage thoracique, doivent maintenir activement leur volume pulmonaire de fin d’expiration (VPFE). Ceci se fait par interruption précoce de l’expiration, et par le freinage expiratoire au niveau laryngé et par la persistance de la contraction des muscles inspiratoires. Chez les nourrissons ventilés mécaniquement, notre équipe a montré que le diaphragme est activé jusqu’à la fin de l’expiration (activité tonique). Il n’est pas clair si cette activité tonique diaphragmatique compense pour l’absence de freinage laryngé liée à l’intubation endotrachéale. Objectif : Notre objectif est de déterminer si l’activité tonique diaphragmatique persiste après l’extubation chez les nourrissons et si elle peut être observée chez les enfants plus âgés. Méthode : Ceci est une étude observationnelle longitudinale prospective de patients âgés de 1 semaine à 18 ans admis aux soins intensifs pédiatriques (SIP), ventilés mécaniquement pour >24 heures et avec consentement parental. L’activité électrique du diaphragme (AEdi) a été enregistrée à l’aide d’une sonde nasogastrique spécifique à 4 moments durant le séjour aux SIP : en phase aigüe, pré et post-extubation et au congé. L’AEdi a été analysée de façon semi-automatique. L’AEdi tonique a été définie comme l’AEdi durant le dernier quartile de l’expiration. Résultats : 55 patients avec un âge médian de 10 mois (écart interquartile: 1-48) ont été étudiés. Chez les nourrissons (<1an, n=28), l’AEdi tonique en pourcentage de l’activité inspiratoire était de 48% (30-56) en phase aigüe, 38% (25-44) pré-extubation, 28% (17-42) post-extubation et 33% (22-43) au congé des SIP (p<0.05, ANOVA, avec différence significative entre enregistrements 1 et 3-4). Aucun changement significatif n’a été observé pré et post-extubation. L’AEdi tonique chez les patients plus âgés (>1an, n=27) était négligeable en phases de respiration normale (0.6mcv). Par contre, une AEdi tonique significative (>1mcv et >10%) a été observée à au moins un moment durant le séjour de 10 (37%) patients. La bronchiolite est le seul facteur indépendant associé à l’activité tonique diaphragmatique. Conclusion : Chez les nourrissons, l’AEdi tonique persiste après l’extubation et elle peut être réactivée dans certaines situations pathologiques chez les enfants plus âgés. Elle semble être un indicateur de l’effort du patient pour maintenir son VPFE. D’autres études devraient être menées afin de déterminer si la surveillance de l’AEdi tonique pourrait faciliter la détection de situations de ventilation inappropriée.

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.