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.^

Oceanographic investiations from the Sea of Ochotsk

The Sea of Okhotsk is a marginal sea of the Pacific Ocean, which is characterized by strong variations in the productivity and sediment supply due to sea ice transport and river input. Furthermore the variations in the hydrological cycle determine the formation of the SOIW (Sea of Okhotsk Intermediate Water) which plays an important role in the ventilation processes in the intermediate water of the N-Pacific. Isotope data measured on planktonic and benthic foraminifera, sedimentological and geochemical studies of sediment cores and surface samples from the Sea of Okhotsk are used to reconstruct the paleoceanography during the past 350.000 years. The dating and correlation of the sediments are based on oxygen isotope stratigraphy, absolute ages, magnetic susceptibility as well as a detailled tephrachronology of the entire basin. The sedimentation rates are characterized by temporal and spatial variations. The maximum sedimentation rate takes place at the continental slope off Sakhalin due to the input of the Amur River, the sea ice drift and the high productivity. The sedimentation rate in the eastern part of the Sea of Okhotsk is generelly high because of the influence of the nutrient-rich Kamchatka Current. In the central and northern parts of the Sea of Okhotsk, areas with low productivity and reduced terrestrial supply, the sedimentation rate is the lowest. The analyses of the surface sediment samples make it possible to characterize the (sub)- recent sediment supply and transportation processes. The bulk sediment measurements, isotope data and the accumulation rate of ice-rafted debris (IRD) show a dominant sea ice cover and a region with a high productivity as well as a high Amur River input in the western part of the sea. The eastern part of the Sea of Okhotsk, however, is marked by the predominance of warm and nutrient-rich water masses coming from the Kamchatka Current which restricts the sea ice cover. This is reflected in low content of ice-rafted debris and high productivity proxies as well as in isotope data. The deposits of the Sea of Okhotsk are characterized by terrestrial, biogenic and volcanogenic sediment input which varies temporally and spatially. Here, the sedimentation pattern is dominated by the terrestrial input. Bulk sediment measurements and sample analyses of the > 63 micron particle input make it possible to distinguish glacial and interglacial fluctuations. The sedimentation processes during glacial times are determined by a high content of ice-rafted debris, whereas the primary production is higher during interglacial periods. During the last glacial/interglacial cycle the IRD-distribution pattern indicates a strong sea ice transport in the western part and in large areas of the open sea in the eastern part of the Sea of Okhotsk with a relatively constant ice-drift system. The IRD flux in sediments of the oxygen isotope Stage 6 reflects a new sedimentation pattern in the eastern part of the sea. This high IRD accumulation rate indicates ice advances beyond the shelf margin and an iceberg transport from NE-E direction into the Sea of Okhotsk. The several large, brief, negative anomalies in d13C values of Neogloboquadrina pachyderma (s) show releases of methane from basin sediments which correspond to periods of relative sea level falls. The high sedimentation rates on the Sakhalin slope allow insights into the climatic history in Holocene and indicate shorter-scale variations oscillation in Stage 3, which correlate with the global climatic changes. These variations are described as Dansgaard-Oeschger cycles in Greenland ice cores and as Heinrich-Events in several marine sediment cores from the N-Atlantic.

(Table 2) Chemical composition of Fe-Mn nodules and volcanic glass in sediments of the Atlantic Ocean

Distribution pattern of titanium in Quaternary sediments of the Atlantic Ocean are examined on the base of 750 Ti and Fe determinations, and several dozen of complete chemical analyses. Analyses of surface sediment samples and sediment cores up to 6 m long were made. Stratigraphic levels from Middle Pleistocene to Holocene were identified from planktonic foraminifera. Distributions of Ti in recent and Pleistocene deposits were mapped. High titanium contents were found in sediments containing products of basalt vulcanism and in iron-manganese nodules. To determine origin of titanium concentrations in sediments, Ti/Fe ratios were calculated. Maximal values of this ratio were found in areas of basaltic volcanism and of intensive terrigenous sedimentation.

(Table 2) Salinity, pH, alkalinity and major ion concentrations in ANDRILL core AND-2A pore water

The compositional record of the AND-2A drillcore is examined using petrological, sedimentological, volcanological and geochemical analysis of clasts, sediments and pore waters. Preliminary investigations of basement clasts (granitoids and metasediments) indicate both local and distal sources corresponding to variable ice-volume and ice-flow directions. Low abundance of sedimentary clasts (e.g., arkose, litharenite) suggests reduced contributions from sedimentary covers while intraclasts (e.g., diamictite, conglomerate) attest to intrabasinal reworking. Volcanic material includes pyroclasts (e.g., pumice, scoria), sediments and lava. Primary and reworked tephra layers occur within the Early Miocene interval (1093 to 640 metres below sea floor mbsf). The compositions of volcanic clasts reveal a diversity of alkaline types derived from the McMurdo Volcanic Group. Finer-grained sediments (e.g., sandstone, siltstone) show increases in biogenic silica and volcanic glass from 230 to 780 mbsf and higher proportions of terrigenous material c. 350 to 750 mbsf and below 970 mbsf. Basement clast assemblages suggest a dominant provenance from the Skelton Glacier - Darwin Glacier area and from the Ferrar Glacier - Koettlitz Glacier area. Provenance of sand grains is consistent with clast sources. Thirteen Geochemical Units are established based on compositional trends derived from continuous XRF scanning. High values of Fe and Ti indicate terrigenous and volcanic sources, whereas high Ca values signify either biogenic or diagenic sources. Highly alkaline and saline pore waters were produced by chemical exchange with glass at moderately elevated temperatures.

Off-equilibrium fluctuation-dissipation relations in the 3d Ising spin glass in a magnetic field

We study the fluctuation-dissipation relations for a three dimensional Ising spin glass in a magnetic field both in the high temperature phase as well as in the low temperature one. In the region of times simulated we have found that our results support a picture of the low temperature phase with broken replica symmetry, but a droplet behavior cannot be completely excluded.

Universal critical behavior of the two-dimensional Ising spin glass

We use finite size scaling to study Ising spin glasses in two spatial dimensions. The issue of universality is addressed by comparing discrete and continuous probability distributions for the quenched random couplings. The sophisticated temperature dependency of the scaling fields is identified as the major obstacle that has impeded a complete analysis. Once temperature is relinquished in favor of the correlation length as the basic variable, we obtain a reliable estimation of the anomalous dimension and of the thermal critical exponent. Universality among binary and Gaussian couplings is confirmed to a high numerical accuracy.

Phytochemical-loaded mesoporous silica nanoparticles for nose-to-brain olfactory drug delivery

Central nervous system (CNS) drug delivery is often hampered due to the insidious nature of the blood-brain barrier (BBB). Nose-to-brain delivery via olfactory pathways have become a target of attention for drug delivery due to bypassing of the BBB. The antioxidant properties of phytochemicals make them promising as CNS active agents but possess poor water solubility and limited BBB penetration. The primary aim of this study was the development of mesoporous silica nanoparticles (MSNs) loaded with the poorly water-soluble phytochemicals curcumin and chrysin which could be utilised for nose-to-brain delivery. We formulated spherical MSNP using a templating approach resulting in ∼220nm particles with a high surface porosity. Curcumin and chrysin were successfully loaded into MSNP and confirmed through Fourier transformation infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and HPLC approaches with a loading of 11-14% for curcumin and chrysin. Release was pH dependant with curcumin demonstrating increased chemical stability at a lower pH (5.5) with a release of 53.2%±2.2% over 24h and 9.4±0.6% for chrysin. MSNP were demonstrated to be non-toxic to olfactory neuroblastoma cells OBGF400, with chrysin (100μM) demonstrating a decrease in cell viability to 58.2±8.5% and curcumin an IC50 of 33±0.18μM. Furthermore confocal microscopy demonstrated nanoparticles of <500nm were able to accumulate within cells with FITC-loaded MSNP showing membrane localised and cytoplasmic accumulation following a 2h incubation. MSNP are useful carriers for poorly soluble phytochemicals and provide a novel vehicle to target and deliver drugs into the CNS and bypass the BBB through olfactory drug delivery.

Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Elemental Analysis of Glass and Ink by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Laser Induced Breakdown Spectroscopy (LIBS)

The necessity of elemental analysis techniques to solve forensic problems continues to expand as the samples collected from crime scenes grow in complexity. Laser ablation ICP-MS (LA-ICP-MS) has been shown to provide a high degree of discrimination between samples that originate from different sources. In the first part of this research, two laser ablation ICP-MS systems were compared, one using a nanosecond laser and another a femtosecond laser source for the forensic analysis of glass. The results showed that femtosecond LA-ICP-MS did not provide significant improvements in terms of accuracy, precision and discrimination, however femtosecond LA-ICP-MS did provide lower detection limits. In addition, it was determined that even for femtosecond LA-ICP-MS an internal standard should be utilized to obtain accurate analytical results for glass analyses. In the second part, a method using laser induced breakdown spectroscopy (LIBS) for the forensic analysis of glass was shown to provide excellent discrimination for a glass set consisting of 41 automotive fragments. The discrimination power was compared to two of the leading elemental analysis techniques, µXRF and LA-ICP-MS, and the results were similar; all methods generated >99% discrimination and the pairs found indistinguishable were similar. An extensive data analysis approach for LIBS glass analyses was developed to minimize Type I and II errors en route to a recommendation of 10 ratios to be used for glass comparisons. Finally, a LA-ICP-MS method for the qualitative analysis and discrimination of gel ink sources was developed and tested for a set of ink samples. In the first discrimination study, qualitative analysis was used to obtain 95.6% discrimination for a blind study consisting of 45 black gel ink samples provided by the United States Secret Service. A 0.4% false exclusion (Type I) error rate and a 3.9% false inclusion (Type II) error rate was obtained for this discrimination study. In the second discrimination study, 99% discrimination power was achieved for a black gel ink pen set consisting of 24 self collected samples. The two pairs found to be indistinguishable came from the same source of origin (the same manufacturer and type of pen purchased in different locations). It was also found that gel ink from the same pen, regardless of the age, was indistinguishable as were gel ink pens (four pens) originating from the same pack.

Color reflectance and XRF drill core scanner data of ANDRILL core AND-2A

The compositional record of the AND-2A drillcore is examined using petrological, sedimentological, volcanological and geochemical analysis of clasts, sediments and pore waters. Preliminary investigations of basement clasts (granitoids and metasediments) indicate both local and distal sources corresponding to variable ice-volume and ice-flow directions. Low abundance of sedimentary clasts (e.g., arkose, litharenite) suggests reduced contributions from sedimentary covers while intraclasts (e.g., diamictite, conglomerate) attest to intrabasinal reworking. Volcanic material includes pyroclasts (e.g., pumice, scoria), sediments and lava. Primary and reworked tephra layers occur within the Early Miocene interval (1093 to 640 metres below sea floor mbsf). The compositions of volcanic clasts reveal a diversity of alkaline types derived from the McMurdo Volcanic Group. Finer-grained sediments (e.g., sandstone, siltstone) show increases in biogenic silica and volcanic glass from 230 to 780 mbsf and higher proportions of terrigenous material c. 350 to 750 mbsf and below 970 mbsf. Basement clast assemblages suggest a dominant provenance from the Skelton Glacier - Darwin Glacier area and from the Ferrar Glacier - Koettlitz Glacier area. Provenance of sand grains is consistent with clast sources. Thirteen Geochemical Units are established based on compositional trends derived from continuous XRF scanning. High values of Fe and Ti indicate terrigenous and volcanic sources, whereas high Ca values signify either biogenic or diagenic sources. Highly alkaline and saline pore waters were produced by chemical exchange with glass at moderately elevated temperatures.

The Effect of Foam Core Density on the Flexural and Axial Behaviour of Sandwich Panels of Varying Slenderness with Natural Flax-FRP and Glass-FRP Composite Skins

This study investigates the effect of foam core density and skin type on the behaviour of sandwich panels as structural beams tested in four-point bending and axially compressed columns of varying slenderness and skin thickness. Bio-composite unidirectional flax fibre-reinforced polymer (FFRP) is compared to conventional glass-FRP (GFRP) as the skin material used in conjunction with three polyisocyanurate (PIR) foam cores with densities of 32, 64 and 96 kg/m3. Eighteen 1000 mm long flexural specimens were fabricated and tested to failure comparing the effects of foam core density between three-layer FFRP skinned and single-layer GFRP skinned panels. A total of 132 columns with slenderness ratios (kLe/r) ranging from 22 to 62 were fabricated with single-layer GFRP skins, and one-, three-, and five-layer FFRP skins for each of the three foam core densities. The columns were tested to failure in concentric axial compression using pinned-end conditions to compare the effects of each material type and panel height. All specimens had a foam core cross-section of 100x50 mm with 100 mm wide skins of equal thickness. In both flexural and axial loading, panels with skins comprised of three FFRP layers showed equivalent strength to those with a single GFRP layer for all slenderness ratios and core densities examined. Doubling the core density from 32 to 64 kg/m3 and tripling the density to 96 kg/m3 led to flexural strength increases of 82 and 213%, respectively. Both FFRP and GFRP columns showed a similar variety of failure modes related to slenderness. Low slenderness of 22-25 failed largely due to localized single skin buckling, while those with high slenderness of 51-61 failed primarily by global buckling followed by secondary skin buckling. Columns with intermediate slenderness experienced both localized and global failure modes. High density foam cores more commonly exhibited core shear failure. Doubling the core density of the columns resulted in peak axial load increases, across all slenderness ratios, of 73, 56, 72 and 71% for skins with one, three and five FFRP layers, and one GFRP layer, respectively. Tripling the core density resulted in respective peak load increases of 116, 130, 176 and 170%.

Novel P(3HB) Composite Films Containing Bioactive Glass Nanoparticles for Wound Healing Applications

Bioactive glass (BG) is considered an ideal material for haemostasis as it releases Ca2+ ions upon hydration, which is required to support thrombosis. In this study the effect of the presence of the BG nanoparticles in P(3HB) microsphere films on the structural properties, thermal properties and biocompatibility of the films were studied. The nanoscaled bioactive glass with a high surface area was also tested for its in vitro haemostatic efficacy and was found to be able to successfully reduce the clot detection time. In an effort to study the effect of the roughness induced by the formation of HA on the cellular functions such as cell adhesion, cell mobility and cell differentiation, the composite films were immersed in SBF for a period of 1, 3 and 7 days. From the SEM images the surface of the P(3HB)/n-BG composite microsphere films appeared fairly uniform and smooth on day 1, however on day 3 and day 7 a rough and uneven surface was observed. The presence of HA on the composite microsphere films on day 3 and day 7 influenced the surface roughness of the films. However, when the P(3HB)/n-BG composite microspheres with enhanced surface roughness were tested for biocompatibility, reduced amount of protein adsorption and cell adhesion were observed. This study thus revealed that there is an optimal surface roughness for the P(3HB) microsphere films for increased cell adhesion, beyond which it could be deleterious for cell adhesion and differentiation.

Measurement of electromagnetic pulses generated during interactions of high power lasers with solid targets

A target irradiated with a high power laser pulse, blows off a large amount of charge and as a consequence the target itself becomes a generator of electromagnetic pulses (EMP) owing to high return current flowing to the ground through the target holder. The first measurement of the magnetic field induced by the neutralizing current reaching a value of a few kA was performed with the use of an inductive target probe at the PALS Laser Facility (Cikhardt et al. Rev. Sci. Instrum. 85 (2014) 103507). A full description of EMP generation should contain information on the spatial distribution and temporal variation of the electromagnetic field inside and outside of the interaction chamber. For this reason, we consider the interaction chamber as a resonant cavity in which different modes of EMP oscillate for hundreds of nanoseconds, until the EMP is transmitted outside through the glass windows and EM waves are attenuated. Since the experimental determination of the electromagnetic field distribution is limited by the number of employed antennas, a mapping of the electromagnetic field has to be integrated with numerical simulations. Thus, this work reports on a detailed numerical mapping of the electromagnetic field inside the interaction chamber at the PALS Laser Facility (covering a frequency spectrum from 100 MHz to 3 GHz) using the commercial code COMSOL Multiphysics 5.2. Moreover we carried out a comparison of the EMP generated in the parallelepiped-like interaction chamber used in the Vulcan Petawatt Laser Facility at the Rutherford Appleton Laboratory, against that produced in the spherical interaction chamber of PALS.

Use of a Neural Network to Predict Strength and Optimum Compositions of Natural Alumina-Silica-Based Geopolymers

In order to predict compressive strength of geopolymers prepared from alumina-silica natural products, based on the effect of Al 2 O 3 /SiO 2, Na 2 O/Al 2 O 3, Na 2 O/H 2 O, and Na/[Na+K], more than 50 pieces of data were gathered from the literature. The data was utilized to train and test a multilayer artificial neural network (ANN). Therefore a multilayer feedforward network was designed with chemical compositions of alumina silicate and alkali activators as inputs and compressive strength as output. In this study, a feedforward network with various numbers of hidden layers and neurons were tested to select the optimum network architecture. The developed three-layer neural network simulator model used the feedforward back propagation architecture, demonstrated its ability in training the given input/output patterns. The cross-validation data was used to show the validity and high prediction accuracy of the network. This leads to the optimum chemical composition and the best paste can be made from activated alumina-silica natural products using alkaline hydroxide, and alkaline silicate. The research results are in agreement with mechanism of geopolymerization.


Read More: http://ascelibrary.org/doi/abs/10.1061/(ASCE)MT.1943-5533.0000829