ATR characterisation of synergistic corrosion inhibition of mild steel surfaces by cerium salicylate

The nature of deposits on mild steel surfaces formed by exposure to corrosive and inhibiting solutions has been examined by attenuated total reflectance spectroscopy. For cerium-based inhibitors, e.g. CeCl₃ the formation of cerium-containing coatings was detected whilst the cerium carboxylate Ce(sal)₃ (sal=salicylate), which combines the Ce³⁺ with the known organic inhibitor sal⁻, was shown to involve substantial deposition of both cerium and a salicylate species. These results, combined with corrosion inhibition data for the respective inhibitor compounds clearly indicate a synergistic corrosion mechanism for Ce(sal)₃ which underpins the improved performance of this corrosion inhibitor in comparison to the individual components (i.e. Na(sal) or CeCl₃).

ATR FT-IR absorption enhancement of a thin film under the photon-tunneling condition

A simple, yet very powerful technique for the spectral acquisition of an extremely thin film with enhanced absorption was explored. An infrared absorption of an extremely thin film confined between media of high refractive indices was greater than that of its bulk when the spectrum was acquired under the attenuated total reflection (ATR) condition with parallel (p) polarized radiation. The absorption enhancement was not observed under perpendicular (s) polarized radiation. Theoretical investigations indicated that the absorption enhancement was proportional to the integration of the mean square evanescent field within the film. The field integration under p-polarized radiation increased, while that under s-polarized radiation decreased as the thickness of the confined film became thinner. The maximum enhancement was observed when the film was sufficiently thinner than the penetration depth. The phenomena were experimentally investigated, and the results agreed very well with theoretical predictions.

Rapid determination of protein contents in microencapsulated fish oil supplements by ATR-FTIR spectroscopy and partial least square regression (PLSR) analysis

Following the recent success in quantitative analysis of essential fatty acid compositions in a commercial microencapsulated fish oil (?EFO) supplement, we extended the application of portable attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic technique and partial least square regression (PLSR) analysis for rapid determination of total protein contents-the other major component in most commercial ?EFO powders. In contrast to the traditional chromatographic methodology used in a routine amino acid analysis (AAA), the ATR-FTIR spectra of the ?EFO powder can be acquired directly from its original powder form with no requirement of any sample preparation, making the technique exceptionally fast, noninvasive, and environmentally friendly as well as being cost effective and hence eminently suitable for routine use by industry. By optimizing the spectral region of interest and number of latent factors through the developed PLSR strategy, a good linear calibration model was produced as indicated by an excellent value of coefficient of determination R2 = 0.9975, using standard ?EFO powders with total protein contents in the range of 140-450 mg/g. The prediction of the protein contents acquired from an independent validation set through the optimized PLSR model was highly accurate as evidenced through (1) a good linear fitting (R2 = 0.9759) in the plot of predicted versus reference values, which were obtained from a standard AAA method, (2) lowest root mean square error of prediction (11.64 mg/g), and (3) high residual predictive deviation (6.83) ranked in very good level of predictive quality indicating high robustness and good predictive performance of the achieved PLSR calibration model. The study therefore demonstrated the potential application of the portable ATR-FTIR technique when used together with PLSR analysis for rapid online monitoring of the two major components (i.e., oil and protein contents) in finished ?EFO powders in the actual manufacturing setting.

Impact of the new business tax system (alienation of personal services income) Act 2000

The implications of categorising income as "personal services income" and the actual meaning of this term have been marked with uncertainty. The Commissioner of Taxation has long asserted that "personal services income" inherently may not be derived by an entity other than the person whose exertions produce the income. In Liedig v FCT (1994) 28 ATR 141, however, Hill J held that in the absence of a specific legislative provision, there was no basis for the Commissioner's doctrine. The specific legislative measures Hill J required were put in place through the New Business Tax System (Alienation of Personal Services Income) Act 2000. In certain circumstances this Act prevents interposed entities from deriving personal services income. Such payments are attributed instead to the individual who performs the services.

It will also be seen, however, that these provisions do not apply to entities that are conducting a "personal services business". It is submitted that the combined effect of, inter alia, the Act's definition of "personal services income" and "personal services business" is to give the Act a narrower scope than the Commissioner's personal services doctrine. Moreover, it will be submitted that the statutory definition of personal services income also suffers from the same flaws that Hill J identified as relevant to the Commissioner's personal services doctrine.

The effects of dye dopants on the conductivity and optical absorption properties of polypyrrole

Ten anionic compounds, including four acidic dyes, were used to dope polypyrrole powder. The effects of the dopants on density, optical absorption and conductivity of the polypyrroles were studied. The presence of the dopant in the conducting polymer matrix was verified by ATR-FTIR spectroscopy. Density function theory (DFT) simulation was used to understand the effect of the dopants on the solid structure, optical absorption and energy band structures. Anthraquinone-2-sulfonic acid-doped polypyrrole yielded the highest conductivity. The dye-doped polypyrrole showed an enhancement in its UV–vis optical absorption.

A morphology-related study on photodegradation of protein fibres

The wool fibre has a complex morphology, consisting of an outer layer of cuticle scales surrounding an inner cortex. These two components are hard to separate effectively except by using harsh chemical treatments, making it difficult to determine the susceptibility of the different components of the fibre to photoyellowing. An approach to this problem based on mechanical fibre modification is described. To expose the inner cortex of wool to different degrees, clean wool fibres were converted into ‘powders’ of various fineness via mechanical chopping, air-jet milling, ball milling or their combination. Four types of powdered wool (samples A, B, C and D) were produced with reducing particle size distributions and an increasing level of surface damage as observed using SEM. Sample A contained essentially intact short fibre snippets and sample D contained a large amount of exposed cortical materials. Samples B and C contained a mixture of short fibre snippets and cortical materials. Solid wool discs were then compressed from the corresponding powder samples in a polished stainless steel die to enable colour measurement and UV irradiation studies. ATR-FTIR studies on powder discs demonstrated a small shift in the amide I band from 1644 cm−1 for disc A to 1654 cm−1 for disc D due to the different structures of the wool cuticle and cortex, in agreement with previous studies. Similarly an increase in the intensity ratio of the amide I to amide II band (1540 cm−1) was observed for disc D, which contains a higher fraction of cortical material at the surface of the disc.

Discs prepared from sample D appeared the lightest in colour before exposure and had the slowest photoyellowing rate, whereas discs made from powders A–C with a higher level of cuticle coverage were more yellow before exposure and experienced a faster rate of photoyellowing. This suggests that the yellow chromophores of wool may be more prevalent in cuticle scales, and that wool photoyellowing occurs to a greater extent in the cuticle than in the cortex. Photo-induced chemiluminescence measurements showed that sample D had a higher chemiluminescence intensity after exposure to UVA radiation and a faster decay rate than samples A and B. Thus one of the roles of the wool cuticle may be to protect the cortex by quenching of free radical oxidation during exposure to the UV wavelengths present in sunlight.

Determination of trans fatty acid levels by FTIR in processed foods in Australia

Health authorities around the world advise ‘limiting consumption of trans   fatty acids’, however in Australia the trans fatty acid (TFA) content is not  required to be listed in the nutrition information panel unless a declaration or nutrient claim is made about fatty acids or cholesterol. Since there is limited knowledge about trans fatty acid levels in processed foods available in Australia, this study aimed to determine the levels of TFA in selected food items known to be sources of TFA from previously published studies. Food items (n=92) that contain vegetable oil and a total fat content greater than 5% were included. This criterion was used in conjunction with a review of similar studies where food items were found to contain high levels of trans fatty acids. Lipids were extracted using solvents. Gravimetric methods were used to determine total fat content and trans fatty acid levels were quantified by Attenuated Total Reflectance Fourier Transform Infrared spectroscopy. High levels of trans fatty acids were found in certain items in the Australian food supply, with a high degree of variability. Of the samples analysed, 13  contained greater than 1 g of trans fatty acids per serving size, the highest value was 8.1 g/serving. Apart from when the nutrition information panel states that the content is less than a designated low level, food labels sold in Australia do not indicate trans fatty acid levels. We suggested that health authorities seek ways to assist consumers to limit their intakes of trans fatty acids.

Influence of helium atmospheric plasma treatment on surface and fracture-mechanical behaviour of quickstepTM cured bio-composites

This work investigated the potential of improving flexural properties of natural fiber (jute) reinforced biocomposites by atmospheric pressure helium plasma treatment. Composites were made by the use of combined hand lay-up and vacuum bagging technique followed by newly developed Australia patented Quickstep^TM curing. The physical properties of helium plasma modified fibers were investigated by means of wettability time, coefficient of friction (COF), atomic force microscopy (AFM) and chemical nature of the surface with ATR-FTIR and XPS. There was found a logical correlation between physical and chemical characteristics of the surface of fiber with the fracture mechanical behavior of their resulting biocomposites. In addition, the use of helium atmospheric plasma treatment prior to Quickstep^TM process has proved to be a potential way to positively alter the fracture-mechanical behavior of biocomposites. This study will lead to new commercial applications of natural fiber jute for the composite industry that go beyond wrapping and packaging.

Pulsed plasma polymerization of hexamethyldisiloxane onto wool : control of moisture vapor transmission rate and surface adhesion

A new fabric with potential in medical textiles has been developed by application of a surface coating on wool using pulsed plasma polymerization of HMDSO. This coating enabled a controllable MVTR and surface adhesion. MVTR in the range recommended for optimum wound healing was obtained by varying frequency, monomer pressure and deposition time. Lower surface adhesion was achieved. Peeling tests, contact angle measurements, SPM force curves and ATR FT-IR were used to characterize the surfaces for both wool and a PE model substrate. All these results were consistent with a decrease in surface energy after PP-HMDSO treatment. ATR FT-IR results showed a siloxane film with less organic Si(CH₃)_n groups and more SiOSi cross-links.

The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors

The corrosion inhibition mechanisms of new cerium and lanthanum cinnamate based compounds have been investigated through the surface characterisation of the steel exposed to NaCl solution of neutral pH. Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to identify the nature of the deposits on the metal surface and demonstrated that after accelerated tests the corrosion product commonly observed on steel (i.e. lepidocrocite, γ-FeOOH) is absent. The cinnamate species were clearly present on the steel surface upon exposure to NaCl solution for short periods and appeared to coordinate through the iron. At longer times the Rare Earth Metal (REM) oxyhydroxide species are proposed to form as identified through the bands in the 1400–1500 cm⁻¹ region. These latter bands have been previously assigned to carbonate species adsorbed onto REM oxyhydroxide surfaces. The protection mechanism appears to involve the adsorption of the REM–cinnamate complex followed by the hydrolysis of the REM to form a barrier oxide on the steel surface.

Protein solubilising and stabilising ionic liquids

We report a family of biocompatible ionic liquids (ILs) which are able to dissolve significant amounts of proteins such as cytochrome c and in which ATR-FTIR spectroscopy results show retention of secondary structure to extreme temperatures.

Mechanism of permanganate chemiluminescence

Spectroscopic and synthetic methods have been exploited to deduce the mechanism for acidic potassium permanganate chemiluminescence. We have employed electron paramagnetic resonance (EPR) spectroscopy with a continuous flow assembly to monitor the formation of radical intermediates in real time generated from substrate oxidation by manganese(VII). These transient species react with manganese(III) in solution to produce the  previously characterized manganese(II)* emission source. Using UV-vis, EPR, attenuated total reflection (ATR)-FTIR, and chemiluminescence spectroscopies, we have established that there are two distinct enhancement mechanisms that in combination afford a 50-fold increase in emission intensity when the reaction is conducted in the presence of phosphate oligomers. In addition to preventing disproportionation of the manganese(III) precursor, the phosphate oligomers form protective "cagelike” structures around the manganese(II)* emitter, thus preventing nonradiative relaxation pathways.

Synthesis, characterization, and multilayer assembly of pH sensitive graphene−polymer nanocomposites

pH sensitive graphene−polymer composites have been prepared by the modification of graphene basal planes with pyrene-terminated poly(2-N,N′-(dimethyl amino ethyl acrylate) (PDMAEA) and poly(acrylic acid) (PAA) via π−π stacking. The pyrene-terminal PDMAEA and PAA were synthesized using reversible addition−fragmentation chain transfer (RAFT) polymerization with a pyrene-functional RAFT agent. The graphene−polymer composites were found to demonstrate phase transfer behavior between aqueous and organic media at different pH values. Atomic force microscopy (AFM) analysis revealed that the thicknesses of the graphene−polymer sheets were approximately 3.0 nm when prepared using PDMAEA (M_n: 6800 and PDI: 1.12). The surface coverage of polymer chains on the graphene basal plane was calculated to be 5.3 × 10⁻¹¹ mol cm⁻² for PDMAEA and 1.3 × 10⁻¹⁰ mol cm⁻² for PAA. The graphene−polymer composites were successfully characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and thermogravimetric analysis (TGA). Self-assembly of the two oppositely charged graphene−polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements.

Symmetrically tapered <30-micron-thick quasi-planar Ge waveguides as chemical sensors for microanalysis

Symmetrically tapered planar IR waveguides have been fabricated by starting with a ZnS coated concave piece of single-crystal Ge, embedding it in an epoxide resin as a supporting substrate, and then grinding and polishing a planar surface until the thickness at the taper minimum is <30 μm. Such tapering is expected to enhance a waveguide's sensitivity as an evanescent wave sensor by maximizing the amount of evanescent wave energy present at the thinnest part of the waveguide. As predicted by theory, the surface sensitivity, i.e., the absorbance signal per molecule in contact with the sensing region, increases with decreasing thickness of the tapered region even while the total energy throughput decreases. The signal-to-noise ratio obtained depends very strongly on the quality of the polished surfaces of the waveguides. The surface sensitivity is superior to that obtained with a commercial Ge attenuated total reflection (ATR) accessory for several types of sample, including thin films (<10 ng) and small volumes (<1 μL) of volatile solvents. By using the waveguides, light-induced structural changes in the protein bacteriorhodopsin were observable using samples as small as ∼50 pmol (∼1 μg). In addition, the waveguide sensors can reveal the surface compositions on a single human hair, pointing to their promise as a tool for forensic fiber analysis.

Novel biorenewable plastics based on natural resources using ionic liquids

We report biorenewable plastics developed from natural resources such as cellulose, wool and microorganismsynthesized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) copolymer [1-3]. Novel materials were prepared by blending these natural polymers in an ionic liquid green solvent, 1-butyl-3-methylimidazolium chloride. Cellulose /PHBV blend materials were successfully prepared in this way. The ionic liquid was completely recycled with high yield and purity after the processing. The blend materials can be processed into different solid forms such as films, noodle-like fibers and bulk blocks. It was found that there exists hydrogen bonding interaction between the components which facilities the mixing of these polymers. The cellulose/PHBV blend materials all show phase-separated structure as revealed by micro ATR-FTIR imaging (Figure 1) and scanning electron microscopy (SEM). The PHBV domains of 6 - 8 µm are distributed in a cellulose matrix at high concentrations of cellulose while the blend materials with high PHBV concentrations exhibit multiphase morphologies, including beadlike PHBV microdomains in the range of 300-400 nm. The dispersion of PHBV in cellulose leads to significant improvement in hydrophobicity due to its beadlike structure. The blend materials represent a class of degradable plastics from natural bioresources using the ionic liquid green solvent.