Matthew R. Rowles

Chemical optimisation of the compressive strength of aluminosilicate geopolymers synthesised by sodium silicate activation of metakaolinite

High strength cements can be synthesised by alkali activation of materials rich in Al2O3 and SiO2. In this study, amorphous aluminosilicate polymers produced by sodium silicate activation of metakaolinite were studied, with particular reference to chemical optimisation of the compressive strength according to the relative concentrations of Si, Al and Na in the polymer. The sodium silicate was manufactured from silica fume and sodium hydroxide. The compressive strengths of polymers with Si∶Al molar ratios of 1.0–3.0 and Na∶Al molar ratios of 0.5–2.0 were considered. The polymers were cured at 75 °C for 24 h and their compressive strengths measured after aging for 7 days. The strength was found to depend systematically on the relative amounts of Si, Al and Na, with the maximum being 64 ± 3 MPa for an Si∶Al∶Na molar ratio of 2.5∶1∶1.3. X-Ray diffraction/scattering data indicate qualitatively that the bonding network in the amorphous aluminosilicate alters systematically with composition.

Atomically Dispersed Transition Metals on Carbon Nanotubes with UltraHigh Loading for Selective Electrochemical Carbon Dioxide Reduction

Single-atom catalysts (SACs) are the smallest entities for catalytic reactions with projected high atomic efficiency, superior activity, and selectivity; however, practical applications of SACs suffer from a very low metal loading of 1-2 wt%. Here, a class of SACs based on atomically dispersed transition metals on nitrogen-doped carbon nanotubes (MSA-N-CNTs, where M = Ni, Co, NiCo, CoFe, and NiPt) is synthesized with an extraordinarily high metal loading, e.g., 20 wt% in the case of NiSA-N-CNTs, using a new multistep pyrolysis process. Among these materials, NiSA-N-CNTs show an excellent selectivity and activity for the electrochemical reduction of CO2 to CO, achieving a turnover frequency (TOF) of 11.7 s-1 at -0.55 V (vs reversible hydrogen electrode (RHE)), two orders of magnitude higher than Ni nanoparticles supported on CNTs.

CONVAS2 : A program for the merging of diffraction data

A computer program is presented that allows for the merging of diffraction patterns collected at multiple positions on the Powder Diffraction beamline of the Australian Synchrotron. It is also generally applicable to detector systems based on other modular detectors. The program allows for the interpolation of data to a constant 2θ step size and to normalise intensities to beam current and/or monitor count rate.

Fluoride substitution in sodium hydride for thermal energy storage applications

The solid-state solutions of NaHxF1−x (x = 1, 0.95, 0.85, 0.5) have been investigated to determine their potential for thermal energy applications. Thermal analyses of these materials have determined that an increase in fluorine content increases the temperature of hydrogen release, with a maximum rate of desorption at 443 °C for NaH0.5F0.5 compared to 408 °C for pure NaH, while pressure–composition–isotherm measurements have established a ΔHdes of 106 ± 5 kJ mol−1 H2 and ΔSdes of 143 ± 5 J K−1 mol−1 H2, compared to 117 kJ mol−1 H2 and 167 J K−1 mol−1 H2, respectively, for pure NaH. While fluorine substitution actually leads to a decrease in the stability (enthalpy) compared to pure NaH, it has a larger depressing effect on the entropy that leads to reduced hydrogen equilibrium pressures. In situ powder X-ray diffraction studies have ascertained that decomposition occurs via enrichment of fluorine in the NaHxF1−x composites while, unlike pure NaH, rehydrogenation is easily achievable under mild pressures. Further, cycling studies have proven that the material is stable over at least seven hydrogen sorption cycles, with only a slight decrease in capacity while operating between 470 and 520 °C. Theoretically, these materials may operate between 470 and 775 °C and, as such, show great potential as thermal energy storage materials for concentrating solar thermal power applications.

Whole-pattern profile fitting of powder diffraction data collected in parallel-beam flat-plate asymmetric reflection geometry

A simple, physically based model that allows the whole-pattern profile fitting of diffraction data collected in parallel-beam flat-plate asymmetric reflection geometry is presented. In this arrangement, there is a fixed angle between the incident beam and the sample, resulting in a fixed-length beam footprint. The use of a wide-angle detector for the simultaneous detection of the data precludes the use of any diffracted beam optics. Therefore, the observed peak widths are a function of the length of the beam footprint on the sample. The model uses up to three refinable parameters, depending on the intensity profile of the beam, to calculate the effect of diffraction angle on the width of all diffracted peaks. The use of this model reduces the total number of parameters required to fit the observed peak widths and shapes, hence leading to increased stability in the profile analysis. Implementations of the model are provided for both fundamental parameters and empirical approaches.

Effects of Moisture-Induced Crystallization on the Aerosol Performance of Spray Dried Amorphous Ciprofloxacin Powder Formulations

ABSTRACTPurposeThis study aims to investigate the influence of different storage humidity conditions on crystallization and aerosol performance of inhalable spray dried amorphous powder formulations (Ciprofloxacin hydrochloride as the model drug).MethodsThe spray dried samples were stored at 20%, 55% and 75% relative humidity (RH). Crystallinity was monitored by Powder X-ray diffraction (PXRD), and particle morphology was measured by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Aerosol performance was evaluated using a multi-stage liquid impinger (MSLI).ResultsPXRD diffractograms showed the spray dried Ciprofloxacin stored at 20% RH for three weeks were amorphous; whereas those stored at 55% RH and 75% RH started crystallizing after one hour. Fine particle fraction (FPF) of the particles was improved from 28% to 42% after storage at 55% RH for three days. Such improvement was attributed to the crystallization of amorphous powders, which led to increased particle roughness and reduced particulate contact area, as visualized by SEM and quantified by AFM. A linear relationship was observed between degree of crystallinity/crystallite size and FPF (R2 = 0.94 and R2 = 0.96, respectively). However, deterioration in aerosol performance was observed after storage at 75% RH due to formation of inter-particulate liquid/solid bridges, as confirmed by SEM.ConclusionsThis study provides a fundamental understanding in moisture-induced physical and aerosol instability of the spray dried powder formulations.

Novel synthesis of porous Mg scaffold as a reactive containment vessel for LiBH4

A novel porous Mg scaffold was synthesised and melt-infiltrated with LiBH4 to simultaneously act as both a confining framework and a destabilising agent for H2 release from LiBH4. This porous Mg scaffold was synthesised by sintering a pellet of NaMgH3 at 450 °C under dynamic vacuum. During the sintering process the multi-metal hydride, decomposed to Mg metal and molten Na. The vacuum applied in combination with the applied sintering temperature, created the ideal conditions for the Na to vaporise and to gradually exit the pellet. The pores of the scaffold were created by the removal of the H2 and Na from the body of the NaMgH3 pellet. The specific surface area of the porous Mg scaffold was determined by the Brunauer–Emmett–Teller (BET) method and from Small-Angle X-ray Scattering (SAXS) measurements, which was 26(1) and 39(5) m2 g−1 respectively. The pore size distribution was analysed using the Barrett–Joyner–Halenda (BJH) method which revealed that the majority of the pores were macropores, with only a small amount of mesopores present in the scaffold. The melt-infiltrated LiBH4 was highly dispersed in the porous scaffold according to the morphological observation carried out by a Scanning Electron Microscope (SEM) and also catalysed the formation of MgH2 as seen from the X-ray diffraction (XRD) patterns of the samples after the infiltration process. Temperature Programmed Desorption (TPD) experiments, which were conducted under various H2 backpressures, revealed that the melt-infiltrated LiBH4 samples exhibited a H2 desorption onset temperature (Tdes) at 100 °C which is 250 °C lower than the bulk LiBH4 and 330 °C lower than the bulk 2LiBH4/MgH2 composite. Moreover, the LiH formed during the decomposition of the LiBH4 was itself observed to fully decompose at 550 °C. The as-synthesised porous Mg scaffold acted as a reactive containment vessel for LiBH4 which not only confined the complex metal hydride but also destabilised it by significantly reducing the H2 desorption temperature down to 100 °C.

Aberration corrections for non-Bragg–Brentano diffraction geometries

The construction of peak intensity, profile and displacement aberration functions based on the geometry of a powder diffraction measurement allows for physically realistic corrections to be applied in Rietveld modelling through a fundamental parameters approach. Parallel-beam corrections for asymmetric reflection and Debye–Scherrer geometry are summarized, and corrections for thin-plate transmission are derived and validated. Geometrically correct implementations of preferred orientation models are also summarized.

A capillary specimen aberration for describing X-ray powder diffraction line profiles for convergent, divergent and parallel beam geometries

X-ray powder diffraction patterns of cylindrical capillary specimens have substantially different peak positions, shapes and intensities relative to patterns from flat specimens. These aberrations vary in a complex manner with diffraction angle and instrument geometry. This paper describes a fast numerical procedure that accurately describes the capillary aberration in the equatorial plane for convergent focusing, divergent and parallel beam instrument geometries. Axial divergence effects are ignored and only a cross section of the capillary, a disc, is considered; it is assumed that axial divergence effects can be described using an additional correction that is independent of the disc correction. Significantly, the present implementation uses the TOPAS-Academic aberration approximation technique of averaging nearby aberrations in 2θ space to approximate in-between aberrations, which results in no more than ∼30 disc aberrations calculated over the entire 2θ range, even when the diffraction pattern comprises thousands of peaks. Finally, the disc aberration is convoluted with the emission profile and other instrument and specimen aberrations in a Rietveld refinement sense, allowing for refinement on the specimens absorption coefficient and capillary diameter, as well as the instrument focal length. Large differences between refined and expected values give insight into instrument alignment.

Complex hydrides as thermal energy storage materials: characterisation and thermal decomposition of Na2Mg2NiH6

Complex transition metal hydrides have been identified as being materials for multi-functional applications holding potential as thermal energy storage materials, hydrogen storage materials and optical sensors. Na2Mg2NiH6 (2Na+·2Mg2+·2H−·[NiH4]4−) is one such material. In this study, the decomposition pathway and thermodynamics have been explored for the first time, revealing that at 225 °C, hydrogen desorption commences with two major decomposition steps, with maximum H2 desorption rates at 278 and 350 °C as measured by differential scanning calorimetry. The first step of decomposition results in the formation of Mg2NiHx (x < 0.3) and NaH, before these compounds decompose into Mg2Ni and Na, respectively. PCI analysis of Na2Mg2NiH6 has determined the thermodynamics of decomposition for the first step to have a ΔHdes and ΔSdes of 83 kJ mol−1 H2 and 140 J K−1 mol−1 H2, respectively. Hydrogen cycling of the first step has been achieved for 10 cycles without any significant reduction in hydrogen capacity, with complete hydrogen desorption within 20 min at 395 °C. Despite the relatively high cost of Ni, the ability to effectively store hydrogen reversibly at operational temperatures of 318–568 °C should allow this material to be considered as a thermal energy storage material.