Vibrational spectroscopic studies of wool

Fourier transfonn (FT) Raman, Raman microspectroscopy and Fourier transform infrared (FTIR) spectroscopy have been used for the structural analysis and characterisation of untreated and chemically treated wool fibres. For FT -Raman spectroscopy novel methods of sample presentation have been developed and optimised for the analysis of wool. No significant fluorescence was observed and the spectra could be obtained routinely. The stability of wool keratin to the laser source was investigated and the visual and spectroscopic signs of sample damage were established. Wool keratin was found to be extremely robust with no signs of sample degradation observed for laser powers of up to 600 m W and for exposure times of up to seven and half hours. Due to improvements in band resolution and signal-to-noise ratio, several previously unobserved spectral features have become apparent. The assignment of the Raman active vibrational modes of wool have been reviewed and updated to include these features. The infrared spectroscopic techniques of attenuated total reflectance (ATR) and photoacoustic (P A) have been used to examine shrinkproofed and mothproofed wool samples. Shrinkproofing is an oxidative chemical treatment used to selectively modifY the surface of a wool fibre. Mothproofing is a chemical treatment applied to wool for the prevention of insect attack. The ability of PAS and A TR to vary the penetration depth by varying certain instrumental parameters was used to obtain spectra of the near surface regions of these chemically treated samples. These spectra were compared with those taken with a greater penetration depth, which therefore represent more of the bulk wool sample. The PA and ATR spectra demonstrated that oxidation was restricted to the near-surface layer of wool. Extensive curve fitting of ATR spectra of untreated wool indicated that cuticle was composed of a mixed protein conformation, but was predominately that of an a.-helix. The cortex was proposed to be a mixture of both a.helical and ~-pleated sheet protein conformations. These findings were supported by PAS depth profiling results. Raman microspectroscopy was used in an extensive investigation of the molecular structure of the wool fibre. This included determining the orientation of certain functional groups within the wool fibre and the symmetry of particular vibrations. The orientation ofbonds within the wool fibre was investigated by orientating the wool fibre axis parallel and then perpendicular to the plane of polarisation of the electric vector of the incident radiation. It was experimentally determined that the majority of C=O and N-H bonds of the peptide bond of wool lie parallel to the fibre axis. Additionally, a number of the important vibrations associated with the a-helix were also found to lie parallel to the fibre axis. Further investigation into the molecular structure of wool involved determining what effect stretching the wool fibre had on bond orientation. Raman spectra of stretched and unstretched wool fibres indicated that extension altered the orientation ofthe aromatic rings, the CH2 and CH3 groups of the amino acids. Curve fitting results revealed that extension resulted in significant destruction of the a-helix structure a substantial increase in the P-pleated sheet structure. Finally, depolarisation ratios were calculated for Raman spectra. The vibrations associated with the aromatic rings of amino acids had very low ratios which indicated that the vibrations were highly symmetrical.

Crystal structure of N,N-diethylbenzene-1,4-diaminium dinitrate

In the structure of the title compound, (C10H18N2)2+, 2(NO3)-, the nitrate salt of 4-(N,N-diethylamino)aniline, the two ethyl groups lie almost perpendicular to the plane of the benzene ring [ring to ethyl C-C-N-C torsion angles, -59.5(2) and 67.5(3)deg.]. The aminium groups of the cation form inter-species N-H...O hydrogen bonds with the nitro O-atoms of both anions giving one-dimensional chains extending along c and are extended into a two-dimensional network structure lying parallel to (010). Weak C-H...O hydrogen-bonding associations are also present.

Concurrent multi-scale modeling of civil infrastructures for analyses on structural deterioration—Part I : Modeling methodology and strategy

This paper aims to develop the methodology and strategy for concurrent finite element modeling of civil infrastructures at the different scale levels for the purposes of analyses of structural deteriorating. The modeling strategy and method were investigated to develop the concurrent multi-scale model of structural behavior (CMSM-of-SB) in which the global structural behavior and nonlinear damage features of local details in a large complicated structure could be concurrently analyzed in order to meet the needs of structural-state evaluation as well as structural deteriorating. In the proposed method, the “large-scale” modeling is adopted for the global structure with linear responses between stress and strain and the “small-scale” modeling is available for nonlinear damage analyses of the local welded details. A longitudinal truss in steel bridge decks was selected as a case to study how a CMSM-of-SB was developed. The reduced-scale specimen of the longitudinal truss was studied in the laboratory to measure its dynamic and static behavior in global truss and local welded details, while the multi-scale models using constraint equations and substructuring were developed for numerical simulation. The comparison of dynamic and static response between the calculated results by different models indicated that the proposed multi-scale model was found to be the most efficient and accurate. The verification of the model with results from the tested truss under the specific loading showed that, responses at the material scale in the vicinity of local details as well as structural global behaviors could be obtained and fit well with the measured results. The proposed concurrent multi-scale modeling strategy and implementation procedures were applied to Runyang cable-stayed bridge (RYCB) and the CMSM-of-SB of the bridge deck system was accordingly constructed as a practical application.

Porohyperelastic analysis to explore mechanical properties of chondrocytes using numerical modeling and experiments : a finite element study

There are many continuum mechanical models have been developed such as liquid drop models, solid models, and so on for single living cell biomechanics studies. However, these models do not give a fully approach to exhibit a clear understanding of the behaviour of single living cells such as swelling behaviour, drag effect, etc. Hence, the porohyperelastic (PHE) model which can capture those aspects would be a good candidature to study cells behaviour (e.g. chondrocytes in this study). In this research, an FEM model of single chondrocyte cell will be developed by using this PHE model to simulate Atomic Force Microscopy (AFM) experimental results with the variation of strain rate. This material model will be compared with viscoelastic model to demonstrate the advantages of PHE model. The results have shown that the maximum value of force applied of PHE model is lower at lower strain rates. This is because the mobile fluid does not have enough time to exude in case of very high strain rate and also due to the lower permeability of the membrane than that of the protoplasm of chondrocyte. This behavior is barely observed in viscoelastic model. Thus, PHE model is the better model for cell biomechanics studies.

A vibrational spectroscopic study of philipsbornite PbAl3(AsO4)2(OH)5⋅H2O-molecular structural implications and relationship to the crandallite subgroup arsenates

The presence of arsenic in the environment is a hazard. The accumulation of arsenate by a range of cations in the formation of minerals provides a mechanism for the remediation of arsenate contamination. The formation of the crandallite group of minerals provides a mechanism for arsenate accumulation. Among the crandallite minerals are philipsbornite, arsenocrandallite and arsenogoyazite. Raman spectroscopy complimented with infrared spectroscopy has enabled aspects of the structure of philipsbornite to be studied. The Raman spectrum of philipsbornite displays an intense band at around 840 cm−1 attributed to the overlap of the symmetric and antisymmetric stretching modes. Raman bands observed at 325, 336, 347, 357, 376 and 399 cm−1 are assigned to the ν2 (AsO4)3− symmetric bending vibration (E) and to the ν4 bending vibration (F2). The observation of multiple bending modes supports the concept of a reduction in symmetry of the arsenate anion in philipsbornite. Evidence for phosphate in the mineral is provided. By using an empirical formula, hydrogen bond distances for the OH units in philipsbornite of 2.8648 Å, 2.7864 Å, 2.6896 Å cm−1 and 2.6220 were calculated.

Effects of joint thickness, adhesion and web shells to the face shell bedded concrete masonry loaded in compression

The Australian masonry standard allows either prism tests or correction factors based on the block height and mortar thickness to evaluate masonry compressive strength. The correction factor helps the taller units with conventional 10 mm mortar being not disadvantaged due to size effect. In recent times, 2-4 mm thick, high-adhesive mortars and H blocks with only the mid-web shell are used in masonry construction. H blocks and thinner and higher adhesive mortars have renewed interest of the compression behaviour of hollow concrete masonry and hence is revisited in this paper. This paper presents an experimental study carried out to examine the effects of the thickness of mortar joints, the type of mortar adhesives and the presence of web shells in the hollow concrete masonry prisms under axial compression. A non-contact digital image correlation technique was used to measure the deformation of the prisms and was found adequate for the determination of strain fi eld of the loaded face shells subjected to axial compression. It is found that the absence of end web shells lowers the compressive strength and stiffness of the prisms and the thinner and higher adhesive mortars increase the compressive strength and stiffness, while lowering the Poisson's ratio. © Institution of Engineers Australia, 2013.

State-of-the-art of the Australian thin bed concrete structural masonry

With a view to minimising the spiraling labour costs, the concrete masonry industry is developing thin layer mortar technology (known as thin bed technology) collaboratively with Queensland University of Technology. Similar technologies are practiced in Europe mainly for clay brick masonry; in the UK thin layer mortared concrete masonry has been researched under commercial contract with limited information published. This paper presents numerous experimental data generated over the past three years. It is shown that this form of masonry requires special drymixed mortar containing a minimum of 2% polymer for improved workability and blocks with tighter height tolerance, both of which might increase the cost of these constituent materials. However, through semiskilled labour, tools to dispense and control the thickness of mortar and the associated increase in productivity, reduction to the overall costs of this form of construction can be achieved. Further the polymer mortar provides several advantages: (1) improved sustainability due to dry curing and (2) potential to construct mortar layers of 2mm thickness and (3) ability for mechanisation of mortar application and control of thickness without the need for skilled labour.

Numerical modeling of railway track supporting system using finite–infinite and thin layer elements

The present contribution deals with the numerical modelling of railway track-supporting systems-using coupled finite-infinite elements-to represent the near and distant field stress distribution, and also employing a thin layer interface element to account for the interfacial behaviour between sleepers and ballast. To simulate the relative debonding, slipping and crushing at the contact area between sleepers and ballast, a modified Mohr-Coulomb criterion was adopted. Further more an attempt was made to consider the elasto plastic materials’ non-linearity of the railway track supporting media by employing different constitutive models to represent steel, concrete and other supporting materials. It is seen that during an incremental-iterative mode of load application, the yielding initially started from the edge of the sleepers and then flowed vertically downwards and spread towards the centre of the railway supporting system.

Improvements to the design of Litesteel Beams undergoing lateral distortional buckling

An Australian manufacturer has recently developed an innovative group of cold-formed steel hollow flange sections, one of them is LiteSteel Beams (LSBs). The LSB sections are produced from thin and high strength steels by a patented manufacturing process involving simultaneous cold-forming and dual electric resistance welding. They have a unique geometry consisting of rectangular hollow flanges and a relatively slender web. The LSB flexural members are subjected to lateral distortional buckling effects and hence their capacities are reduced for intermediate spans. The current design rules for lateral distortional buckling were developed based on the lower bound of numerical and experimental results. The effect of LSB section geometry was not considered although it could influence the lateral distortional buckling performance. Therefore an accurate finite element model of LSB flexural members was developed and validated using experimental and finite strip analysis results. It was then used to investigate the effect of LSB geometry. The extensive moment capacity data thus developed was used to develop improved design rules for LSBs with one of them considering the LSB geometry effects through a modified slenderness parameter. The use of the new design rules gave higher lateral distortional buckling capacities for LSB sections with intermediate slenderness. The new design rule is also able to accurately predict the lateral distortional buckling moment capacities of other hollow flange beams (HFBs).

An application of near-infrared and mid-infrared spectroscopy to the study of selected minerals

Near-infrared spectroscopy is a somewhat unutilised technique for the study of minerals. The technique has the ability to determine water content, hydroxyl groups and transition metals. In this paper we show the application of NIR spectroscopy to the study of selected minerals. The structure and spectral properties of two Cu-tellurite minerals graemite and teineite are compared with bismuth containing tellurite mineral smirnite by the application of NIR and IR spectroscopy. The position of Cu2+ bands and their splitting in the electronic spectra of tellurites are in conformity with octahedral geometry distortion. The spectral pattern of smirnite resembles graemite and the observed band at 10855 cm-1 with a weak shoulder at 7920 cm-1 is identified as due to Cu2+ ion. Any transition metal impurities may be identified by their bands in this spectral region. Three prominent bands observed in the region of 7200-6500 cm-1 are the overtones of water whilst the weak bands observed near 6200 cm-1in tellurites may be attributed to the hydrogen bonding between (TeO3)2- and H2O. The observation of a number of bands centred at around 7200 cm-1 confirms molecular water in tellurite minerals. A number of overlapping bands in the low wavenumbers 4500-4000 cm-1 is the result of combinational modes of (TeO3)2−ion. The appearance of the most intense peak at 5200 cm-1 with a pair of weak bands near 6000 cm-1 is a common feature in all the spectra and is related to the combinations of OH vibrations of water molecules, and bending vibrations ν2 (δ H2O). Bending vibrations δ H2O observed in the IR spectra shows a single band for smirnite at 1610 cm-1. The resolution of this band into number of components is evidenced for non-equivalent types of molecular water in graemite and teineite. (TeO3)2- stretching vibrations are characterized by three main absorptions at 1080, 780 and 695 cm-1.

Improvements to the fire performance of light gauge steel floor systems

Light gauge steel frame (LSF) structures are increasingly used in commercial and residential buildings because of their non-combustibility, dimensional stability and ease of installation. A common application is in floor-ceiling systems. The LSF floor-ceiling systems must be designed to serve as fire compartment boundaries and provide adequate fire resistance. Fire-rated floor-ceiling assemblies have been increasingly used in buildings. However, limited research has been undertaken in the past and hence a thorough understanding of their fire resistance behaviour is not available. Recently a new composite floor-ceiling system has been developed to provide higher fire rating. But its increased fire rating could not be determined using the currently available design methods. Therefore a research project was conducted to investigate its structural and fire resistance behaviour under standard fire conditions. This paper presents the results of full scale experimental investigations into the structural and fire behaviour of the new LSF floor system protected by the composite ceiling unit. Both the conventional and the new floor systems were tested under structural and fire loads. It demonstrates the improvements provided by the new composite panel system in comparison to conventional floor systems. Numerical studies were also undertaken using the finite element program ABAQUS. Measured temperature profiles of floors were used in the numerical analyses and their results were compared with fire test results. Tests and numerical studies provided a good understanding of the fire behaviour of the LSF floor-ceiling systems and confirmed the superior performance of the new composite system.

An application of near-infrared and mid-infrared spectroscopy to the study of natural halotrichites : halotrichite, apjohnite and wupatkiite

Near-infrared (NIR) and Fourier transform infrared (FTIR) spectroscopy have been used to determine the mineralogical character of isomorphic substitutions for Mg2+ by divalent transition metals Fe, Mn, Co and Ni in natural halotrichite series. The minerals are characterised by d-d transitions in NIR region 12000-7500 cm-1. NIR spectrum of halotrichite reveals broad feature from 12000 to 7500 cm-1 with a splitting of two bands resulting from ferrous ion transition 5T2g ® 5Eg. The presence of overtones of OH- fundamentals near 7000 cm-1 confirms molecular water in the mineral structure of the halotrichite series. The appearance of the most intense peak at around 5132 cm-1 is a common feature in the three minerals and is derived from combination of OH- vibrations of water molecules and 2 water bending modes. The influence of cations like Mg2+, Fe2+, Mn2+, Co2+, Ni2+ shows on the spectra of halotrichites. Especially wupatkiite-OH stretching vibrations in which bands are distorted conspicuously to low wave numbers at 3270, 2904 and 2454 cm-1. The observation of high frequency 2 mode in the infrared spectrum at 1640 cm-1 indicates coordination of water molecules is strongly hydrogen bonded in natural halotrichites. The splittings of bands in 3 and 4 (SO4)2- stretching regions may be attributed to the reduction of symmetry from Td to C2v for sulphate ion. This work has shown the usefulness of NIR spectroscopy for the rapid identification and classification of the halotrichite minerals.

Development and synthesis of innovative approaches to the surgical assessment of articular cartilage degeneration

This research has established, through ultrasound, near infrared spectroscopy and biomechanics experiments, parameters and parametric relationships that can form the framework for quantifying the integrity of the articular cartilage-on-bone laminate, and objectively distinguish between normal/healthy and abnormal/degenerated joint tissue, with a focus on articular cartilage. This has been achieved by: 1. using traditional experimental methods to produce new parameters for cartilage assessment; 2. using novel methodologies to develop new parameters; and 3. investigating the interrelationships between mechanical, structural and molec- ular properties to identify and select those parameters and methodologies that can be used in a future arthroscopic probe based on points 1 and 2. By combining the molecular, micro- and macro-structural characteristics of the tissue with its mechanical properties, we arrive at a set of critical benchmarking parameters for viable and early-stage non-viable cartilage. The interrelationships between these characteristics, examined using a multivariate analysis based on principal components analysis, multiple linear regression and general linear modeling, could then to deter- mine those parameters and relationships which have the potential to be developed into a future clinical device. Specifically, this research has found that the ultrasound and near infrared techniques can subsume the mechanical parameters and combine to characterise the tissue at the molecular, structural and mechanical levels over the full depth of the cartilage matrix. It is the opinion in this thesis that by enabling the determination of the precise area of in uence of a focal defect or disease in the joint, demarcating the boundaries of articular cartilage with dierent levels of degeneration around a focal defect, better surgical decisions that will advance the processes of joint management and treatment will be achieved. Providing the basis for a surgical tool, this research will contribute to the enhancement and quanti�cation of arthroscopic procedures, extending to post- treatment monitoring and as a research tool, will enable a robust method for evaluating developing (particularly focalised) treatments.