ARTICLE | doi:10.20944/preprints202207.0043.v1
Online: 4 July 2022 (09:26:05 CEST)
THz band-pass filters were fabricated by laser ablation of micro-foils of stainless steel and Kapton. Their spectral performance was tested in transmission and re- flection at the THz beamline at the Australian Synchrotron (AuSy). A 25 μm Kapton film performed as a Fabry-Pérot etalon with a free spectral range of FSR = 119 cm−1, high finesse Fc ≈ 17, and was tuneable over ~10 μm (at ~5 THz band) with β = 30° tilt. The structure of the THz beam focal region as extracted by the first mirror (slit) shows a complex polarisation-wavelength- position dependence across the beam. This is important for polarisation sensitive measurements (in transmission and reflection) and requires normalisation at each orientation of linear polarisation.
ARTICLE | doi:10.20944/preprints202102.0271.v1
Subject: Medicine & Pharmacology, Allergology Keywords: ATR; THz; synchrotron radiation; biological tissues; temperature variation
Online: 11 February 2021 (09:29:43 CET)
A novel method of investigating the temperature dependent variation of aspects of the complex refractive index n* in samples in the THz range using continuous, non-polarised, synchrotron radiation is presented. The method relies on the use of ATR apparatus, and retains the advantage of minimal sample preparation, which is a feature of ATR techniques. The method demonstrates the viability of rapidly monitoring temperature reflectance whilst continuously heating or cooling samples by using a temperature variable Thermal Sample Stage. The method remains useful when the refractive index of the sample precludes attenuated total reflection study. This is demonstrated with the water reflectance experiments. The temperature dependent ATR reflectance of tissue-representative fats (lard and Lurpak® butter) was investigated with the novel approach. Both are within the ATR range of the diamond crystal in a “true” ATR mode. Lard showed no clear temperature variation between -15 0C and 24 0C at 0.7 to 1.15 THz or 1.70 to 2.25 THz. Lard can be regarded as having invariable, constant, dielectric properties within mixtures when biological substances are being assessed for temperature dependent dielectric variation within the stated THz ranges. Lurpak® butter (water content 14.7%) displayed temperature dependent reflectance features with a steady decline in reflectivity with increasing temperature. This is in line with the temperature-dependent behaviour of liquid water. There is no rapid change in reflectance, even at -20 0C, suggesting that emulsified water retains liquid-water-like THz properties at freezing temperatures.
ARTICLE | doi:10.20944/preprints201902.0211.v1
Subject: Physical Sciences, Applied Physics Keywords: Ge(001)-2×1; oxidation; synchrotron radiation photoemission
Online: 22 February 2019 (04:07:19 CET)
Embryo stage of oxidation of an epi Ge(001)-2×1 by atomic oxygen and molecular O2 is studied via synchrotron radiation photoemission. The topmost surface buckled with the up- and down-dimer atoms and the first subsurface layer behave distinctly from the bulk by exhibiting surface core-level shifts in the Ge 3d core-level spectrum. The O2 molecules become dissociated upon reaching the epi Ge(001)-2×1 surface. One of the O atom removes off the up-dimer atom, and the other bonds with the underneath Ge atom in the subsurface layer. Atomic oxygen adsorbed on the epi Ge(001)-2×1 preferentially in between the up-dimer atoms and the underneath subsurface atoms without affecting the down-dimer atoms. The electronic environment of the O-affiliated Ge up-dimer atoms becomes similar to that of the down-dimer atoms. Both exhibit an enrichment in charge, where the subsurface of the Ge layer is maintained in a charge-deficient state. The dipole moment originally generated in the buckled reconstruction no longer exists, thereby resulting in a decrease in the ionization potential. The down-dimer Ge atoms and the back-bonded subsurface atoms remain inert to atomic O and molecular O2, a possible cause of low reliability in Ge-related metal-oxide-semiconductor (MOS) devices.
ARTICLE | doi:10.20944/preprints201809.0359.v1
Subject: Materials Science, Nanotechnology Keywords: synchrotron X-ray diffraction; nano-structures; nano mechanics
Online: 18 September 2018 (16:50:04 CEST)
The three-point bending behavior of a single Au nanowire deformed with an atomic force microscope was monitored by coherent X-ray diffraction using a sub-micrometer sized hard X-ray beam. While three-dimensional reciprocal-space maps were recorded before and after deformation by standard rocking curves, they were measured by scanning the energy of the incident X-ray beam during deformation at different loading stages. The mechanical behavior of the nanowire is visualized in reciprocal space and a complex deformation mechanism is described. In addition to the expected bending of the nanowire, torsion is detected. Bending and torsion angles are quantified from the high resolution diffraction data.
CONCEPT PAPER | doi:10.20944/preprints202106.0505.v1
Subject: Physical Sciences, Acoustics Keywords: ATR, THz, synchrotron radiation, diagnostics, polariscopy, four polarisation method
Online: 21 June 2021 (11:28:36 CEST)
Capabilities of the Attenuated Total Reflection (ATR) at THz wavelengths for increased sub-surface depth characterisation of (bio-)materials is presented. The penetration depth of a THz evanescent wave in biological samples is dependent on the wavelength and temperature and can reach 0.1-0.5 mm depth due to strong refractive index change ∼0.4 of the ice-water transition; this is quite significant and important when studying biological samples. Technical challenges are discussed when using ATR for uneven, heterogeneous, high refractive index samples with possibility of frustrated total internal reflection (a breakdown of the ATR reflection-mode into transmission-mode). Local field enhancements at the interface are discussed with numerical/analytical examples. Maxwell’s scaling was used to model behaviour of absorber-scatterer inside materials at the interface with ATR prism for realistic complex refractive indices of bio-materials. Modality of ATR with polarisation analysis is proposed and its principle illustrated, opening an invitation for its experimental validation. The sensitivity of the polarised ATR mode to the refractive index between the sample and ATR prism is revealed. Design principles of polarisation active optical elements and spectral filters are outlined. The results and concepts are based on experiments carried out at the THz beamline of the Australian Synchrotron.
ARTICLE | doi:10.20944/preprints202012.0558.v1
Subject: Materials Science, Biomaterials Keywords: Microstructure; Titanium Dioxide; Thin Film; Sol-Gel; Synchrotron Radiation Imaging
Online: 22 December 2020 (12:22:13 CET)
Ag/TiO2 thin films were prepared using the sol-gel spin coating method. The microstructural growth behaviors of the prepared Ag/TiO2 thin films were elucidated using real-time synchrotron radiation imaging, its structure determined using grazing incidence X-ray diffraction (GIXRD), its morphology imaged using the field emission scanning electron microscopy (FESEM), and its surface topography examined using the atomic force microscope (AFM) in contact mode. Cubical white spots were detected, identified as Ag, while the TiO2 thin film resembles a porous ring-like structure with each ring coalescing and forming channels. Junction growth is directly proportional with time under continuous heating conditions (annealing), and its growth orientations and patterns were seemingly random.
ARTICLE | doi:10.20944/preprints201903.0127.v1
Subject: Materials Science, Nanotechnology Keywords: focal plane array, thermal source, synchrotron radiation, infrared spectroscopy, hyperspectral imaging, silk, SZ2080
Online: 11 March 2019 (09:38:21 CET)
A focal plane array (FPA) detector was used for hyperspectral imaging in the infrared (IR) spectral region using thermal and synchrotron light sources. FPA Fourier-transform IR (FTIR) imaging microspectroscopy will be able to monitor real time changes at specific absorption bands when combined with high brightness synchrotron source. In this study, several types of samples with unique structural motifs were selected and used for assessing the capability of the FPA-FTIR imaging technique. It was shown that the time required for polariscopy at IR wavelengths can be substantially reduced by the FPA-FTIR imaging approach. By using natural and laser fabricated polymers with sub-wavelength features, alignment of absorbing molecular dipoles was revealed as well as higher order patterns (laser fabricated structures). Micro-spectroscopy of absorber orientation reveals alignment patterns even when they are not spatially resolved.
ARTICLE | doi:10.20944/preprints201710.0140.v1
Subject: Chemistry, Inorganic & Nuclear Chemistry Keywords: chalcogenogallates; polymorphism; solid solutions; in situ X-ray diffraction; synchrotron radiation; rietveld refinement
Online: 20 October 2017 (12:53:24 CEST)
The formation of solid solution series Cs1-xMxGaQ2-mC64 (M = K, Rb; Q = S, Se; x = 0–1) was studied by X-ray diffraction and spectroscopic methods, revealing a complete miscibility of CsGaQ2-mC64 with RbGaQ2 and KGaSe2, and a large miscibility gap with KGaS2. All solid solution members exhibit similar Raman spectra, indicating the covalent Ga-Q bonding character. The similar optical band gaps likewise further contribute to this conclusion. Up to a degree of substitution, these solid solutions undergo a phase transition similar to CsGaQ2-mC64. The influence of the substitution parameter x on phase transition process was investigated in situ using high-temperature X-ray powder diffraction experiments. Phase-pure solid solutions of the high-temperature polymorphs Cs1-xMxGaQ2-mC16 were obtained up to xmax(K) = 0.1 and xmax(Rb) = 0.3. The crystal structures of these new CsGaQ2-mC16 analogous high-temperature phases were refined from synchrotron diffraction data by Rietveld-refinement.
ARTICLE | doi:10.20944/preprints202011.0361.v1
Subject: Earth Sciences, Atmospheric Science Keywords: Cleaning protocol; shell weight; climate reconstruction; synchrotron X-ray microtomography (SμCT); foraminiferal-based proxies
Online: 12 November 2020 (18:19:29 CET)
Paleoclimatic and paleoceanographic studies routinely rely on the usage of foraminiferal calcite through faunal, morphometric and physico-chemical proxies. The application of such proxies presupposes the extraction and cleaning of these biomineralized components from ocean sediments in the most efficient way, a process which is often labor intensive and time consuming. In this respect, in this study we performed a systematic experiment for planktonic foraminiferal specimen cleaning using different chemical treatments and evaluated the resulting data of a Late Quaternary gravity core sample from the Aegean Sea. All cleaning procedures adopted here were made on the basis of their minimum potential bias upon foraminiferal proxies, such as the faunal assemblages, degree of fragmentation, stable isotope composition (δ18O and δ13C) and/or Mg/Ca ratios that are frequently used as proxies for surface-ocean climate parameters (e.g., sea surface temperature, sea surface salinity). Six different protocols were tested, involving washing, sieving, and chemical treatment of the samples with hydrogen peroxide and/or sodium hexametaphosphate (Calgon ®). Single species foraminifera shell weighing was combined with high-resolution Scanning Electron Microscopy (SEM) and synchrotron X-ray Microtomography (SμCT) of the material processed by each of the cleaning protocols, in order to assess the decontamination degree of specimen’s ultrastructure and interior. It appeared that a good compromise between time and cleaning efficiency is the simultaneous treatment of samples with a mixed hydrogen peroxide and Calgon solution, while the most effective way for an almost complete decontaminate of the calcareous components from undesirable sedimentary material is a two-step treatment - initially with hydrogen peroxide and subsequently with Calgon solutions.
ARTICLE | doi:10.20944/preprints201912.0077.v1
Subject: Earth Sciences, Environmental Sciences Keywords: Sub-Saharan Africa; phosphorus XANES; fertilizer microdosing; African leafy vegetables; synchrotron; sustainability; nutrient stewardship
Online: 6 December 2019 (04:48:26 CET)
This study investigated the speciation, transformation and availability of P during indigenous vegetable production by employing a combination of chemical and spectroscopic techniques. The study focused upon sites in two ecozones of SSA, the Dry Savanna (lna, Benin Republic) and Rainforest (Ilesha, Nigeria). Both sites were cultivated with two indigenous vegetable species; local amaranth (Amaranthus cruentus (AV)) and African eggplant (Solanum macrocarpon (SM)). The soils were treated with 5 t/ha poultry manure and urea fertilizer at the rate of 0, 20, 40, 60 and 80 kg N/ha. Soil samples were collected before planting and after harvest. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to determine P speciation in these soils. Quantitative analysis showed that adsorbed and organic P were the two dominant P species in the manure amended Dry Savanna (DS) soils before planting and after harvest in soils cultivated with both AV and SM, with the addition of urea (40 kg N/ha) causing an increase in the organic P form in Dry Savanna soils cultivated with AV. Soils of the Rainforest (RF) cultivated with AV initially had large amounts of apatite P in the manure amended soils prior to planting which was transformed to adsorbed and organic P after harvest. Urea addition to the Rainforest soils shifted the dominant P species from organic P to adsorbed and apatite P, which is likely to limit P availability. Soils cultivated with SM had similar proportions of both organic and adsorbed P forms, with 40 kg N/ha addition slightly increased the proportion of adsorbed P.
ARTICLE | doi:10.20944/preprints202212.0037.v1
Subject: Materials Science, General Materials Science Keywords: Gas Sensor, Adsorbed Oxygen, Tungsten oxide, XPS, UPS, XPEEM, Sensing Mechanism, H2, Metal Oxides, Synchrotron.
Online: 2 December 2022 (02:33:15 CET)
Oxidation reactions on semiconducting metal oxides (SMOs) surfaces have been extensively worked on in catalysis, fuel cells, and sensors. SMOs engaged powerfully in energy-related applications such as batteries, supercapacitors, solid oxide fuel cells (SOFCs), and chemical gas sensors. The deep understanding of SMO surface and oxygen interactions and defect engineering has become significant because all those mentioned applications are based on the adsorption/absorption and consumption/transportation of adsorbed (physisorbed-chemisorbed) oxygen. More understanding of adsorbed oxygen and oxygen vacancies (〖V_O^•,V〗_O^(••)) is needed, as the former is the vital requirement for sensing chemical reactions, while the latter facilitates the replenishment of adsorbed oxygen ions on the surface. We determined the relation between sensor response (sensitivity) and the amounts of adsorbed oxygen ions (O_(2(ads))^-,O_((ads),)^- O_2(ads)^(2-),O_((ads))^(2-)), water/hydroxide groups (H2O/OH^-), oxygen vacancies (〖V_O^•,V〗_O^(••)), and ordinary lattice oxygen ions (O_lattice^(2-)) as a function of temperature. During hydrogen (H2) testing, the different oxidation states (W6+, W5+, and W4+) of WO3 were quantified and correlated with oxygen vacancy formation (〖V_O^•,V〗_O^(••)). We used a combined application of XPS, UPS, XPEEM-LEEM, and chemical, electrical and sensory analysis for H2 sensing. We established a correlation between the H2 sensing mechanism of WO3, sensor signal magnitude, the amount of adsorbed oxygen ions, and sensor testing temperature. This paper also provides a review of the detection, quantification, and identification of different adsorbed oxygen species. The different surface and bulk-sensitive characterization techniques relevant to analyzing the SMOs-based sensor are tabulated, providing the sensor designer with the chemical, physical, and electronic information extracted from each technique.
COMMUNICATION | doi:10.20944/preprints202210.0257.v1
Subject: Physical Sciences, Optics Keywords: Phase imaging, bioimaging; synchrotron; near infrared beam; holography; incoherent optics; chemical imaging; phase retrieval; 3D imaging.
Online: 18 October 2022 (08:28:25 CEST)
Phase imaging of biochemical samples has been demonstrated for the first time at the Infrared Microspectroscopy (IRM) beamline of the Australian Synchrotron using the usually discarded Near-IR (NIR) region of the synchrotron-IR beam. The synchrotron-IR beam at the Australian Synchrotron IRM beamline has a unique fork shaped intensity distribution as a result of the gold coated extraction mirror shape, which includes a central slit for rejection of the intense X-ray beam. The resulting beam configuration makes any imaging task challenging. For intensity imaging, the fork shaped beam is usually tightly focused to a point on the sample plane followed by a pixel-by-pixel scanning approach to record the image. In this study, a pinhole was aligned with one of the lobes of the fork shaped beam and the Airy diffraction pattern was used to illuminate biochemical samples. The diffracted light from the samples was captured using a NIR sensitive lensless camera. A rapid phase-retrieval algorithm was applied to the recorded intensity distributions to reconstruct the phase information corresponding to different planes. The preliminary results are promising to develop multimodal imaging capabilities at the IRM beamline of the Australian Synchrotron.
ARTICLE | doi:10.20944/preprints201810.0490.v1
Subject: Life Sciences, Other Keywords: drug release simulation; disintegration simulation; poorly water soluble drug; mefenamic acid; Noyes-Whitney equation; cellular automata; synchrotron microtomography
Online: 22 October 2018 (11:38:04 CEST)
There are numerous approaches to model an influence of manufacturing parameters on the dissolution and disintegration of solid dosage forms. A modern approach for modelling and simulating complex and heterogeneous systems such as pharmaceutical tablets focuses on computationally-intensive finite-element or discreet element methods. Industrial challenges such as Process Analytical Technology (PAT) and Quality by Design are stimulating computer-based technologies to design, control and improve the quality of pharmaceutical compacts and their performance. In this study the disintegration and dissolution model based on the numerical solutions of the Noyes-Whitney equation and cellular automata supported disintegration model are proposed and evaluated. The results from in vitro release studies of the mefenamic acid formulations were compared to the calculated release patterns from the tablet structures obtained from microtomography experiments and the purely algorithmically created virtual tablets.