Electrochromic properties of TiO2 nanotubes coated with electrodeposited MoO3

Despite a favourable morphology, anodized and ordered TiO2 nanotubes are incapable of showing electrochromic properties in comparison to many other metal oxide counterparts. To tackle this issue, MoO3 of 5 to 15 nm thickness was electrodeposited onto TiO2 nanotube arrays. A homogenous MoO3 coating was obtained and the crystal phase of the electrodeposited coating was determined to be α-MoO3. The electronic and optical augmentations of the MoO3 coated TiO2 platforms were evaluated through electrochromic measurements. The MoO3/TiO2 system showed a 4-fold increase in optical density over bare TiO2 when the thickness of the MoO3 coating was optimised. The enhancement was ascribed to (a) the α-MoO3 coating reducing the bandgap of the composite material, which shifted the band edge of the TiO2 platform, and subsequently increased the charge carrier transfer of the overall system and (b) the layered morphology of α-MoO3 that increased the intercalation probability and also provided direct pathways for charge carrier transfer.

Behaviour and design of crest-fixed profiled steel roof claddings under wind uplift

Profiled steel roof claddings in Australia are commonly made of very thin high tensile steel and are crest-fixed with screw fasteners. At present the design of these claddings is entirely based on testing. In order to improve the understanding of the behaviour of these claddings under wind uplift, and thus the design methods, a detailed investigation consisting of a finite element analysis and laboratory experiments was carried out on two-span roofing assemblies of three common roofing profiles. It was found that the failure of the roof cladding system was due to a local failure (dimpling of crests/pull-through) at the fasteners. This paper presents the details of the investigation, the results and then proposes a design method based on the strength of the screwed connections, for which testing of small-scale roofing models and/or using a simple design formula is recommended.

Wind-resistant low-rise buildings in the tropics

High-wind events such as storms and hurricanes cause severe damage to low-rise building (housing, schools, and industrial, commercial, and farm buildings). Roof claddings often suffer the worst, which then leads to accelerated damage to the whole building. Australia leads the way in solving this international problem through extensive research and development work, and has adequate documents in place. This paper first illustrates briefly the nature of high-wind events and then the commonly observed damage to buildings. Australian research work and design practice are then described, based on which suitable design recommendations for wind-resistant buildings are presented.

Three-dimensional modeling of steel portal frame buildings

The realistic strength and deflection behavior of industrial and commercial steel portal frame buildings are understood only if the effects of rigidity of end frames and profiled steel claddings are included. The conventional designs ignore these effects and are very much based on idealized two-dimensional (2D) frame behavior. Full-scale tests of a 1212 m steel portal frame building under a range of design load cases indicated that the observed deflections and bending moments in the portal frame were considerably different from those obtained from a 2D analysis of frames ignoring these effects. Three-dimensional (3D) analyses of the same building, including the effects of end frames and cladding, were carried out, and the results agreed well with full-scale test results. Results clearly indicated the need for such an analysis and for testing to study the true behavior of steel portal frame buildings. It is expected that such a 3D analysis will lead to lighter steel frames as the maximum moments and deflections are reduced.

Continuous production of Bi-2212 thick film on silver tape

Bi-2212 thick film on silver tapes are seen as a simple and low cost alternative to high temperature superconducting wires produced by the Powder In Thbe (PIT) technique, particularly in react and wind applications. A rig for the continuous production of Bi-2212 tapes for use in react and wind component manufacture has been developed and commissioned. The rig consists of several sections, each fully automatic, for task specific duties in the production of HTS tape. The major sections are: tape coating, sintering and annealing. High temperature superconducting tapes with engineering critical current densities of 10 kA/cm2 (77 K, self field), and lengths of up to 100 m have been produced using the rig. Properties of the finished tape are discussed and results are presented for current density versus bend radius and applied strain. Depending on tape content and thickness, irreversible strain tirrm varies between 0.04 and 0.1 %. Cyclic bending tests when applied strain does not exceed Eirrm showed negligible reduction in J c along the length of the tape.

Colloidal drug probe : method development and validation for adhesion force measurement using atomic force microscopy

This study demonstrates a novel technique of preparing drug colloid probes to determine the adhesion force between the drug salbutamol sulphate (SS) and the surfaces of polymer microparticles to be used as carriers for the dispersion of drug particles from a dry powder inhaler (DPI) formulation. Initially model silica probes of approximately 4 μm size, similar to a drug particle used in DPI formulations, were coated with a saturated SS solution with the aid of capillary forces acting between the silica probe and the drug solution. The developed method of ensuring a smooth and uniform layer of SS on the silica probe was validated using X-Ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Using the same technique, silica microspheres preattached on the AFM cantilever were coated with SS. The adhesion forces between the silica probe and drug coated silica (drug probe) and polymer surfaces (hydrophilic and hydrophobic) were determined. Our experimental results showed that the technique for preparing the drug probe was robust and can be used to determine the adhesion force between hydrophilic/hydrophobic drug probe and carrier surfaces to gain a better understanding on drug carrier adhesion forces in DPI formulations.

Multidirectional effects of Sr, Mg and Si-containing bioceramic coatings with high bonding strength on inflammation, osteoclastogenesis and osteogenesis

Ideal coating materials for implants should be able to induce excellent osseointegration, which requires several important parameters, such as good bonding strength, limited inflammatory reaction, balanced osteoclastogenesis and osteogenesis, to gain well-functioning coated implants with long-term life span after implantation. Bioactive elements, like Sr, Mg and Si, have been found to play important roles in regulating the biological responses. It is of great interest to combine bioactive elements for developing bioactive coatings on Ti-6Al-4V orthopedic implants to elicit multidirectional effects on the osseointegration. In this study, Sr, Mg and Si-containing bioactive Sr2MgSi2O7 (SMS) ceramic coatings on Ti-6Al-4V were successfully prepared by plasma-spray coating method. The prepared SMS coatings have significantly higher bonding strength (~37MPa) than conventional pure hydroxyapatite (HA) coatings (mostly in the range of 15-25 MPa). It was also found that the prepared SMS coatings switch the macrophage phenotype into M2 extreme, inhibiting the inflammatory reaction via the inhibition of Wnt5A/Ca2+ and Toll-like receptor (TLR) pathways of macrophages. In addition, the osteoclastic activities were also inhibited by SMS coatings. The expression of osteoclastogenesis related genes (RANKL and MCSF) in bone marrow derived mesenchymal cells (BMSCs) with the involvement of macrophages was decreased, while OPG expression was enhanced on SMS coatings compared to HA coatings, indicating that SMS coatings also downregulated the osteoclastogenesis. However, the osteogenic differentiation of BMSCs with the involvement of macrophages was comparable between SMS and HA coatings. Therefore, the prepared SMS coatings showed multidirectional effects, such as improving bonding strength, reducing inflammatory reaction and downregulating osteoclastic activities, but maintaining a comparable osteogenesis, as compared with HA coatings. The combination of bioactive elements of Sr, Mg and Si into bioceramic coatings can be a promising method to develop bioactive implants with multifunctional properties for orthopaedic application.

Sensitive methods for studying the environmental performance of protective coatings

The safe working lifetime of a structure in a corrosive or other harsh environment is frequently not limited by the material itself but rather by the integrity of the coating material. Advanced surface coatings are usually crosslinked organic polymers such as epoxies and polyurethanes which must not shrink, crack or degrade when exposed to environmental extremes. While standard test methods for environmental durability of coatings have been devised, the tests are structured more towards determining the end of life rather than in anticipation of degradation. We have been developing prognostic tools to anticipate coating failure by using a fundamental understanding of their degradation behaviour which, depending on the polymer structure, is mediated through hydrolytic or oxidation processes. Fourier transform infrared spectroscopy (FTIR) is a widely-used laboratory technique for the analysis of polymer degradation and with the development of portable FTIR spectrometers, new opportunities have arisen to measure polymer degradation non-destructively in the field. For IR reflectance sampling, both diffuse (scattered) and specular (direct) reflections can occur. The complexity in these spectra has provided interesting opportunities to study surface chemical and physical changes during paint curing, service abrasion and weathering, but has often required the use of advanced statistical analysis methods such as chemometrics to discern these changes. Results from our studies using this and related techniques and the technical challenges that have arisen will be presented.

Paint spray mass spectrometry for the detection of additives from polymers on conducting surfaces

Paint Spray is developed as a direct sampling ionisation method for mass spectrometric analysis of additives in polymer-based surface coatings. The technique simply involves applying an external high voltage (5 kV) to the wetted sample placed in front of the mass spectrometer inlet and represents a much simpler ionisation technique compared to those currently available. The capabilities of Paint Spray are demonstrated herein with the detection of four commercially available hindered amine light stabilisers; TINUVIN® 770, TINUVIN® 292, TINUVIN® 123 and TINUVIN® 152 directly from thermoset polyester-based coil coatings. Paint Spray requires no sample preparation or pre-treatment and combined with its simplicity - requiring no specialised equipment - makes it ideal for use by non-specialists. The application of Paint Spray for industrial use has significant potential as sample collection from a coil coating production line and Paint Spray ionisation could enable fast quality control screening at high sensitivity.

Development of optical ray tracing model of a standard parabolic trough collector

Parabolic trough concentrator collector is the most matured, proven and widespread technology for the exploitation of the solar energy on a large scale for middle temperature applications. The assessment of the opportunities and the possibilities of the collector system are relied on its optical performance. A reliable Monte Carlo ray tracing model of a parabolic trough collector is developed by using Zemax software. The optical performance of an ideal collector depends on the solar spectral distribution and the sunshape, and the spectral selectivity of the associated components. Therefore, each step of the model, including the spectral distribution of the solar energy, trough reflectance, glazing anti-reflection coating and the absorber selective coating is explained and verified. Radiation flux distribution around the receiver, and the optical efficiency are two basic aspects of optical simulation are calculated using the model, and verified with widely accepted analytical profile and measured values respectively. Reasonably very good agreement is obtained. Further investigations are carried out to analyse the characteristics of radiation distribution around the receiver tube at different insolation, envelop conditions, and selective coating on the receiver; and the impact of scattered light from the receiver surface on the efficiency. However, the model has the capability to analyse the optical performance at variable sunshape, tracking error, collector imperfections including absorber misalignment with focal line and de-focal effect of the absorber, different rim angles, and geometric concentrations. The current optical model can play a significant role in understanding the optical aspects of a trough collector, and can be employed to extract useful information on the optical performance. In the long run, this optical model will pave the way for the construction of low cost standalone photovoltaic and thermal hybrid collector in Australia for small scale domestic hot water and electricity production.

Ultrasensitive strain sensors made from metal-coated carbon nanofiller/epoxy composites

A set of resistance-type strain sensors has been fabricated from metal-coated carbon nanofiller (CNF)/epoxy composites. Two nanofillers, i.e., multi-walled carbon nanotubes and vapor growth carbon fibers (VGCFs) with nickel, copper and silver coatings were used. The ultrahigh strain sensitivity was observed in these novel sensors as compared to the sensors made from the CNFs without metal-coating, and conventional strain gauges. In terms of gauge factor, the sensor made of VGCFs with silver coating is estimated to be 155, which is around 80 times higher than that in a metal-foil strain gauge. The possible mechanism responsible for the high sensitivity and its dependence with the networks of the CNFs with and without metal-coating and the geometries of the CNFs were thoroughly investigated.

Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip-based nanospray mass spectrometry

RATIONALE: Polymer-based surface coatings in outdoor applications experience accelerated degradation due to exposure to solar radiation, oxygen and atmospheric pollutants. These deleterious agents cause undesirable changes to the aesthetic and mechanical properties of the polymer, reducing its lifetime. The use of antioxidants such as hindered amine light stabilisers (HALS) retards these degradative processes; however, mechanisms for HALS action and polymer degradation are poorly understood. METHODS: Detection of the HALS TINUVINW123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) and the polymer degradation products directly from a polyester-based coil coating was achieved by liquid extraction surface analysis (LESA) coupled to a triple quadrupole QTRAPW 5500 mass spectrometer. The detection of TINUVINW123 and melamine was confirmed by the characteristic fragmentation pattern observed in LESA-MS/MS spectra that was identical to that reported for authentic samples. RESULTS: Analysis of an unstabilised coil coating by LESA-MS after exposure to 4 years of outdoor field testing revealed the presence of melamine (1,3,5-triazine-2,4,6-triamine) as a polymer degradation product at elevated levels. Changes to the physical appearance of the coil coating, including powder-like deposits on the coating's surface, were observed to coincide with melamine deposits and are indicative of the phenomenon known as polymer ' blooming'. CONCLUSIONS: For the first time, in situ detection of analytes from a thermoset polymer coating was accomplished without any sample preparation, providing advantages over traditional extraction-analysis approaches and some contemporary ambient MS methods. Detection of HALS and polymer degradation products such as melamine provides insight into the mechanisms by which degradation occurs and suggests LESA-MS is a powerful new tool for polymer analysis. Copyright (C) 2012 John Wiley & Sons, Ltd.

Desorption electrospray ionisation mass spectrometry reveals in situ modification of a hindered amine light stabiliser resulting from direct N–OR bond cleavage

Detection and characterisation of structural modifications of a hindered amine light stabiliser (HALS) directly from a polyester-based coil coating have been achieved by desorption electrospray ionisation mass spectrometry (DESI-MS) for the first time. In situ detection is made possible by exposing the coating to an acetone vapour atmosphere prior to analysis. This is a gentle and non-destructive treatment that allows diffusion of analyte to the surface without promoting lateral migration. Using this approach a major structural modification of the HALS TINUVIN®123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) was discovered where one N-ether piperidine moiety (N-OC8H17) is converted to a secondary piperidine (N–H). With the use of 2-dimensional DESI-MS imaging the modification was observed to arise during high curing temperatures (ca. 260 °C) and under simulated physiological conditions (80 °C, full solar spectrum). It is proposed that the secondary piperidine derivative is a result of a highly reactive aminyl radical intermediate produced by N–O homolytic bond cleavage. The nature of the bond cleavage is also suggested by ESR spin-trapping experiments employing α-phenyl-N-tert-butyl nitrone (PBN) in toluene at 80 °C. The presence of a secondary piperidine derivative in situ and the implication of N–OR competing with NO–R bond cleavage suggest an alternative pathway for generation of the nitroxyl radical—an essential requirement in anti-oxidant activity that has not previously been described for the N-ether sub-class of HALS.

A novel route in bone tissue engineering : magnetic biomimetic scaffolds

In recent years, interest in tissue engineering and its solutions has increased considerably. In particular, scaffolds have become fundamental tools in bone graft substitution and are used in combination with a variety of bio-agents. However, a long-standing problem in the use of these conventional scaffolds lies in the impossibility of re-loading the scaffold with the bio-agents after implantation. This work introduces the magnetic scaffold as a conceptually new solution. The magnetic scaffold is able, via magnetic driving, to attract and take up in vivo growth factors, stem cells or other bio-agents bound to magnetic particles. The authors succeeded in developing a simple and inexpensive technique able to transform standard commercial scaffolds made of hydroxyapatite and collagen in magnetic scaffolds. This innovative process involves dip-coating of the scaffolds in aqueous ferrofluids containing iron oxide nanoparticles coated with various biopolymers. After dip-coating, the nanoparticles are integrated into the structure of the scaffolds, providing the latter with magnetization values as high as 15 emu g�1 at 10 kOe. These values are suitable for generating magnetic gradients, enabling magnetic guiding in the vicinity and inside the scaffold. The magnetic scaffolds do not suffer from any structural damage during the process, maintaining their specific porosity and shape. Moreover, they do not release magnetic particles under a constant flow of simulated body fluids over a period of 8 days. Finally, preliminary studies indicate the ability of the magnetic scaffolds to support adhesion and proliferation of human bone marrow stem cells in vitro. Hence, this new type of scaffold is a valuable candidate for tissue engineering applications, featuring a novel magnetic guiding option.

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.