The effect of metamictization on the Raman spectroscopy of the uranyl titanate mineral davidite (La,Ce)(Y,U,Fe2+)(Ti,Fe3+)20(O,OH)38

Raman spectra of the uranyl titanate mineral davidite-(La) (La,Ce)(Y,U,Fe2+)(Ti,Fe3+)20(O,OH)38 were analysed and related to the mineral structure. Observed bands are attributed to the TiO and (UO2)2+ stretching and bending vibrations, U-OH bending vibrations, H2O and (OH)- stretching, bending and libration modes. U-O bond lengths in uranyls and O-H…O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of davidite-(La) are in harmony with those of the uranyl oxyhydroxides. The mineral davidite-(La) is metamict as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader.

Dussertite BaFe3+3(AsO4)2(OH)5 : a Raman spectroscopic study of a hydroxy-arsenate mineral

The mineral dussertite, a hydroxy-arsenate mineral of formula BaFe3+3(AsO4)2(OH)5, has been studied by Raman complimented with infrared spectroscopy. The spectra of three minerals from different origins were investigated and proved quite similar, although some minor differences were observed. In the Raman spectra of Czech dussertite, four bands are observed in the 800 to 950 cm-1 region. The bands are assigned as follows: the band at 902 cm-1 is assigned to the (AsO4)3- ν3 antisymmetric stretching mode, at 870 cm-1 to the (AsO4)3- ν1 symmetric stretching mode, and both at 859 cm-1 and 825 cm-1 to the As-OM2+/3+ stretching modes/and or hydroxyls bending modes. Raman bands at 372 and 409 cm-1 are attributed to the ν2 (AsO4)3- bending mode and the two bands at 429 and 474 cm-1 are assigned to the ν4 (AsO4)3- bending mode. An intense band at 3446 cm-1 in the infrared spectrum and a complex set of bands centred upon 3453 cm-1 in the Raman spectrum are attributed to the stretching vibrations of the hydrogen bonded (OH)- units and/or water units in the mineral structure. The broad infrared band at 3223 cm-1 is assigned to the vibrations of hydrogen bonded water molecules. Raman spectroscopy identified Raman bands attributable to (AsO4)3- and (AsO3OH)2- units.

Raman spectroscopic study of the mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 : a mineral of archaeological significance

The mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 is named after the ancient city of Thorikos, in the region of Attica, where the ancient mine sites dating back to the bronze ages are found. Raman spectra of the antimonate bearing mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 were studied, and related to the structure of the mineral. Two intense Raman peaks are observed at 596 and 730 cm-1 and are assigned to the Sb3+O3 and As3+O3 stretching vibrations. A peak at 1085 cm-1 is assigned to the Sb3+OH deformation mode. Raman band at 325 cm-1 is assigned to an OAsO bending vibration of the As3+O3 units and the bands at 269 and 275 cm-1 are attributed to the OSbO bending modes of the Sb3+O3 units. The intense Raman bands at 112 and 133 cm-1 are associated with PbCl stretching modes. Minerals such as nealite and thorikosite are minerals of archaeological significance. Yet no spectroscopic studies of these minerals have been undertaken.

The mineral nealite Pb4Fe2+(AsO3)2Cl4•2H2O : a Raman spectroscopic study

The mineral nealite Pb4Fe2+(AsO3)2Cl4•2H2O is of archaeological significance as it is man made mineral formed through the dumping of mine wastes in the sea. The mineral has been studied by Raman spectroscopy. Raman spectroscopy identifies intense Raman bands at 708 and 732 cm-1 assigned to AsO33- stretching vibrations. In addition low intensity bands are observed at 604 and 632 cm-1 which are attributed to As2O42- symmetric and antisymmetric stretching modes. Low intensity Raman band is observed at 831 cm-1 and is assigned to the AsO44- stretching vibration. Intense Raman bands at 149 and 183 cm-1 are attributed to M-Cl stretching vibrations. Raman spectroscopy identifies arsenic anions in different oxidation states in the mineral. The molecular structure of the mineral nealite, as indicated by Raman spectroscopy, is more complex than has been reported by previous studies.

Application of infrared emission spectroscopy to the thermal transition of indium hydroxide to indium oxide nanocubes

Cubic indium hydroxide nanomaterials were obtained by a low temperature soft-chemical method without any surfactants. The transition of nano-cubic indium hydroxide to cubic indium oxide during dehydroxylation has been studied by infrared emission spectroscopy. The spectra are related to the structure of the materials and the changes in the structure upon thermal treatment. The infrared absorption spectrum of In(OH)3 is characterised by an intense OH deformation band at 1150 cm-1 and two O-H stretching bands at 3107 and 3221 cm-1. In the infrared emission spectra, the hydroxyl-stretching and hydroxyl-bending bands diminish dramatically upon heating, and no intensity remains after 200 °C. However, new low intensity bands are found in the OH deformation region at 915 cm-1 and in OH stretching region at 3437 cm-1. These bands are attributed to the vibrations of newly formed InOH bonds because of the release and transfer of protons during calcination of the nanomaterial. The use of infrared emission spectroscopy enables the low-temperature phase transition brought about through dehydration of In(OH)3 nanocubes to be studied.

Raman spectroscopic study of a hydroxy-arsenate mineral containing bismuth-atelestite Bi2O(OH)(AsO4)

The Raman spectrum of atelestite Bi2O(OH)(AsO4), a hydroxy-arsenate mineral containing bismuth, has been studied in terms of spectra-structure relations. The studied spectrum is compared with the Raman spectrum of atelestite downloaded from the RRUFF database. The sharp intense band at 834 cm-1 is assigned to the 1 AsO43- (A1) symmetric stretching mode and the three bands at 767, 782 and 802 cm-1 to the 3 AsO43- antisymmetric stretching modes. The bands at 310, 324, 353, 370, 395, 450, 480 and 623 cm-1 are assigned to the corresponding ν4 and ν2 bending modes and Bi-O-Bi (vibration of bridging oxygen) and Bi-O (vibration of non-bridging oxygen) stretching vibrations. Lattice modes are observed at 172, 199 and 218 cm-1. A broad low intensity band at 3095 cm-1 is attributed to the hydrogen bonded OH units in the atelestite structure. A weak band at 1082 cm-1 is assigned to  (Bi-OH) vibration.

rac-Ammonium cis-2-carboxycyclohexane-1-carboxylate

In the structure of the title compound, cis NH4+ C8H11O4-, the carboxylic acid and carboxyl groups of the cation adopt C-C-C-O torsion angles of 174.9(2) and -145.4(2)deg. respecticely with the alicyclic ring. The ammonium H atoms of the cations give a total of five hydrogen-bonding associations with carboxyl O-atom acceptors of the anion which, together with a carboxylic acid O-H...O(carboxyl) interaction give two-dimensional sheet structures which lie in the (101) planes in the unit cell.

A Raman spectroscopic study of the antimony mineral klebelsbergite Sb4O4(OH)2(SO4)

Many minerals based upon antimonite and antimonate anions remain to be studied. Most of the bands occur in the low wavenumber region, making infrared spectroscopy difficult to use. This problem can be overcome by using Raman spectroscopy. Raman spectra of the mineral klebelsbergite Sb4O4(OH)2(SO4) were studied, and related to the structure of the mineral. Raman bands observed at 971 cm-1 and a series of overlapping bands are observed at 1029, 1074, 1089, 1139 and 1142 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Two Raman bands are observed at 662 and 723 cm-1 and assigned to the SbO ν3 antisymmetric and ν1 symmetric stretching modes. The intense Raman bands at 581, 604 and 611 cm-1 are assigned to the ν4 SO42- bending modes. Two overlapping bands at 481 and 489 cm-1 are assigned to the ν2 SO42- bending mode. Low intensity bands at 410, 435 and 446 cm-1 may be attributed to OSbO bending modes. The Raman band at 3435 cm-1 is attributed to the OH stretching vibration of the OH units. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the klebelsbergite structure. It is proposed that two sulphate anions are distorted to different extents in the klebelsbergite structure.

Raman spectroscopy of hydrogene-arsenate group (AsO3OH) in solid-state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2•H2O

Raman spectrum of burgessite, Co2(H2O)4[AsO3OH]2.H2O was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO3) and As-OH units together with the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O-H...O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO3OH)2- units in the crystal structure of burgessite was proved in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison.

A Near-infrared and Raman spectroscopic study of the mineral richelsdorfite Ca2Cu5Sb[Cl|(OH)6|(AsO4)4]•6H2O

Raman spectroscopy has enabled insights into the molecular structure of the richelsdorfite Ca2Cu5Sb[Cl|(OH)6|(AsO4)4]·6H2O. This mineral is based upon the incorporation of arsenate or phosphate with chloride anion into the structure and as a consequence the spectra reflect the bands attributable to these anions, namely arsenate or phosphate and chloride. The richelsdorfite Raman spectrum reflects the spectrum of the arsenate anion and consists of ν1 at 849, ν2 at 344 cm−1, ν3 at 835 and ν4 at 546 and 498 cm−1. A band at 268 cm−1 is attributed to CuO stretching vibration. Low wavenumber bands at 185 and 144 cm−1 may be assigned to CuCl TO/LO optic vibrations.

Infrared and infrared emission spectroscopy of nesquehonite Mg(OH)(HCO3)•2H2O : implications for the formula of nesquehonite

The mineral nesquehonite Mg(OH)(HCO3)•2H2O has been analysed by a combination of infrared (IR) and infrared emission spectroscopy (IES). Both techniques show OH vibrations, both stretching and deformation modes. IES proves the OH units are stable up to 450°C. The strong IR band at 934 cm-1 is evidence for MgOH deformation modes supporting the concept of HCO3- units in the molecular structure. Infrared bands at 1027, 1052 and 1098 cm-1 are attributed to the symmetric stretching modes of HCO3- and CO32- units. Infrared bands at 1419, 1439, 1511, and 1528 cm-1 are assigned to the antisymmetric stretching modes of CO32- and HCO3- units. IES supported by thermoanalytical results defines the thermal stability of nesquehonite IES defines the changes in the molecular structure of nesquehonite with temperature. The results of IR and IES supports the concept that the formula of nesquehonite is better defined as Mg(OH)(HCO3)•2H2O.

Raman spectroscopy of hydrogen arsenate group (AsO3OH)2− in solid-state compounds: cobalt-containing zinc arsenate mineral, koritnigite (Zn,Co)(AsO3OH)·H2O

Raman spectra of two well-defined types of koritnigite crystals from the Jáchymov ore district, Czech Republic, were recorded and interpreted. No substantial differences were observed between both crystal types. Observed Raman bands were attributed to the (AsO3OH)2- stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Non-interpreted Raman spectra of koritnigite from the RRUFF database, and published infrared spectra of cobaltkoritnigite were used for comparison. The O-H...O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2- units in the crystal structure of koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

Infrared spectroscopic study of halloysite-potassium acetate intercalation complex

Mid-infrared (MIR) and near-infrared (NIR) spectroscopy have been used to study the molecular structure of halloysite and potassium acetate intercalated halloysite and to determine the structural changes of halloysite through intercalation. The MIR spectra show all fundamental vibrations including the hydroxyl units, basic aluminosilicate framework and water molecules in the structure of halloysite and its intercalation complex. Comparison between halloysite and halloysite-potassium acetate intercalation complex shows almost all bands observed for halloysite are also observed for halloysite-potassium acetate intercalation complex apart from bands observed in the 1700-1300 cm-1 region, but with differences in band intensity. However, NIR, based on MIR spectra, provide sufficient evidence to analyze the structural changes of halloysite through intercalation. There are obvious differences between halloysite and halloysite-potassium acetate intercalation complex in the all spectral ranges. Therefore, the reproducibility of measurement and richness of qualitative information should be simultaneously considered for proper selection of a spectroscopic method for molecular structural analysis.

Vibration characteristics of slender structures under human induced loads

This paper presents the outcome of investigations and studies of the vibratioon characteristics and response of low frequency structural systems for a composite concrete steel floor plate and a reverse profiled cable tensioned foot bridge. These highly dynamic and slender structure are the engineering response to planning, aesthetic and environmental influences, but are prone to excessive and complex vibration. A number of design codes and practice guides provided information to engineers for vibration mitigation However, they are limited to very simple load function applied to a few uncoupled translational modes of excitation. Motivated by the need to address the knowledge gaps in this area, the investigations described in this paper focused on synchronous multi-modal and coupled excitation of the floor plate and footbridge with considerations for torsinal effects. The results showed the potential for adverse dynamic response from multi-modal and coupled excitation influenced by patterned loading, structure geometry, stiffness distribution, directional effects, forcing functions based on activity frequency and duration of foot contact, and modal participation. It was also shown that higher harmonics of the load frequency can excite higher modes in the composite floor structure. Such responsive behaviour is prevalent mainly in slender and lightweight construction and not in stiffer and heavier structural systems. The analytical techniques and methods used in these investigations can supplement the current limited code and best practice provisions for mitigating the impact of human induced vibrations in slender structural systems.

Mechanical conditions in the initial phase of bone healing

Background: Bone healing is sensitive to the initial mechanical conditions with tissue differentiation being determined within days of trauma. Whilst axial compression is regarded as stimulatory, the role of interfragmentary shear is controversial. The purpose of this study was to determine how the initial mechanical conditions produced by interfragmentary shear and torsion differ from those produced by axial compressive movements. ----- ----- Methods: The finite element method was used to estimate the strain, pressure and fluid flow in the early callus tissue produced by the different modes of interfragmentary movement found in vivo. Additionally, tissue formation was predicted according to three principally different mechanobiological theories. ----- ----- Findings: Large interfragmentary shear movements produced comparable strains and less fluid flow and pressure than moderate axial interfragmentary movements. Additionally, combined axial and shear movements did not result in overall increases in the strains and the strain magnitudes were similar to those produced by axial movements alone. Only when axial movements where applied did the non-distortional component of the pressure–deformation theory influence the initial tissue predictions. ----- ----- Interpretation: This study found that the mechanical stimuli generated by interfragmentary shear and torsion differed from those produced by axial interfragmentary movements. The initial tissue formation as predicted by the mechanobiological theories was dominated by the deformation stimulus.