Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

Life Cycle Assessment as a tool to promote sustainable Thermowood boards: a Portuguese case study

The present work aims to develop the Life Cycle Assessment study of thermo-modified Atlanticwood® pine boards based on real data provided by Santos & Santos Madeiras company. Atlanticwood® pine boards are used mainly for exterior decking and cladding facades of buildings. The LCA study is elaborated based on ISO 14040/44 standard and Product Category Rules for preparing an environmental product declaration for Construction Products and Construction Services. The inventory analysis and, subsequently, the impact analysis have been performed using the LCA software SimaPro8.0.4. The method chosen for impact assessment was EPD (2013) V1.01. The results show that more than ¾ of ‘Acidification’, ‘Eutrophication’, ‘Global warming’ and ‘Abiotic depletion’ caused by 1 m3 of Atlanticwood® pine boards production is due to energy consumption (electricity + gas + biomass). This was to be expected since the treatment is based on heat production and no chemicals are added during the heat treatment process.

Elicitors of induced disease resistance in postharvest horticultural crops: a brief review

Increasing loss of conventional fungicides due to pathogen resistance and general unacceptability in terms of public and environmental risk have favoured the introduction of integrated pest management (IPM) programmes. Induction of natural disease resistance (NDR) in harvested horticultural crops using physical, biological and/or chemical elicitors has received increasing attention over recent years, it being considered a preferred strategy for disease management. This article reviews the enhancement of constitutive and inducible antifungal compounds and suppression of postharvest diseases through using elicitors. The effect of timing of pre- and/or postharvest elicitor treatment and environment on the degree of elicitation and the potential for inducing local acquired resistance, systemic acquired resistance and/or induced systemic resistance to reduce postharvest disease is discussed. The review highlights that more applied and basic research is required to understand the role that induced NDR can play in achieving practical suppression of postharvest diseases as part of an IPM approach. (C) 2003 Elsevier B.V. All rights reserved.

Corrosion resistance of aged die cast magnesium alloy AZ91D

The corrosion behaviour of die cast magnesium alloy AZ91D aged at 160degreesC was investigated. The corrosion rate of the alloy decreases with ageing time in the initial stages and then increases again at ageing times greater than 45 h. The dependence of the corrosion rate on ageing time can be related to the changes in microstructure and local composition during ageing. Precipitation of the beta phase (Mg17Al12) occurs exclusively along the grain boundaries during ageing. The beta phase acts as a barrier, resulting in a decreasing corrosion rate in the initial stages of ageing. In the later stages, the decreasing aluminium content of alpha grains makes the alpha matrix more active, causing an increase in the corrosion rate. Electrochemical testing results also confirm the combined effects of the changes in alpha and beta phases on the corrosion resistance of the aged die cast AZ91D alloy. (C) 2003 Elsevier B.V. All rights reserved.

Comparative study of hydrogen storage in Li- and K-doped carbon materials - theoretically revisited

Hydrogen adsorption in alkali-doped carbon materials is investigated theoretically. Our calculations show that hydrogen molecules can be physically adsorbed on alkali-doped graphite at 0 K but such an adsorption is thermodynamically unfavourable. The binding energy of hydrogen adsorption decreases significantly with the increase in temperature and becomes nearly zero at ambient temperature. We suggest that it may be unlikely to observe any hydrogen uptake in alkali-doped carbon materials at or above ambient temperature in the TGA (thermogravimetric) system, the previously reported hydrogen uptake in alkali-doped carbon materials was caused by either uncyclable chemisorbed hydrogen on the defects of carbon (defects were produced by repeated heat treatment) and/or moisture adsorption. (C) 2004 Elsevier Ltd. All rights reserved.

Structure and thermal stability of Langmuir-Blodgett films of barium arachidate

The structures of multilayer Langmuir-Blodgett films of barium arachidate before and after heat treatment have been investigated using both atomic force microscopy (AFM) and grazing incidence synchrotron X-ray diffraction (GIXD). AFM gave information on surface morphology at molecular resolution while GIXD provided quantitative details of the lattice structures of the films with their crystal symmetries and lattice constants. As-prepared films contained three coexisting structures: two triclinic structures with the molecularchains tilted by about 20degrees from the film normal and with 3 x 1 or 2 x 2 super-lattice features arising from height modulation of the molecules in the films; a rectangular structure with molecules perpendicular to the film surface. Of these, the 3 x 1 structure is dominant with a loose correlation between the bilayers. In the film plane both superstructures are commensurate with the local structures, having different oblique symmetries. The lattice constants for the 3 x 1 structure are a(s) = 3a = 13.86 Angstrom, b(s) = b = 4.31 Angstrom and gamma(s) = gamma = 82.7degrees; for the 2 x 2 structure a(s) = 2a = 16.54 Angstrom, b(s) = 2b = 9.67 Angstrom, gamma(s) = gamma = 88degrees. For the rectangular structure the lattice constants are a = 7.39 Angstrom, b = 4.96 Angstrom and gamma = 90degrees. After annealing, the 2 x 2 and rectangular structures were not observed, while the 3 x 1 structure had developed over the entire film. For the annealed films the correlation length in the film plane is about twice that in the unheated films, and in the out-of-plane direction covers two bilayers. The above lattice parameters, determined by GIXD, differed significantly from the values obtained by AFM, due possibly to distortion of the films by the scanning action of the AFM tip. (C) 2004 Published by Elsevier B.V.

Significance of frictional heating for effects of high pressure homogenisation on milk

High pressure homogenisation (HPH) is a novel dairy processing tool, which has many effects on enzymes, microbes, fat globules and proteins in milk. The effects of HPH on milk are due to a combination of shear forces and frictional heating of the milk during processing; the relative importance of these different factors is unclear, and was the focus of this study. The effect of milk inlet temperature (in the range 10-50 degrees C) on residual plasmin, alkaline phosphatase, lactoperoxidase and lipase activities in raw whole bovine milk homogenised at 200 MPa was investigated. HPH caused significant heating of the milk; outlet temperature increased in a linear fashion (0(.)5887 degrees C/degrees C, R-2 =0-9994) with increasing inlet temperature. As milk was held for 20 s at the final temperature before cooling, samples of the same milk were heated isothermally in glass capillary tubes for the same time/temperature combinations. Inactivation profiles of alkaline phosphatase in milk were similar for isothermal heating or HPH, indicating that loss of enzyme activity was due to heating alone. Loss of plasmin and lactoperoxidase activity in HPH milk, however, was greater than that in heated milk. Large differences in residual lipase activities in milks subjected to heating or HPH were observed due to the significant increase in lipase activity in homogenised milk. Denaturation of beta-lactoglobulin was more extensive following HPH than the equivalent heat treatment. Inactivation of plasmin was correlated with increasing fat/serum interfacial area but was not correlated with denaturation of beta-lactoglobulin. Thus, while some effects of HPH on milk are due to thermal effects alone, many are induced by the combination of forces and heating to which the milk is exposed during HPH.

Corrosion resistance of anodised single-phase Mg alloys

This work studied the effect of the impurity iron and the alloying elements aluminium and zinc in single-phase substrate magnesium alloys on the corrosion resistance of the alloys after anodisation. It was found that increasing zinc content (0-2%) led to increased corrosion resistance of an anodised single-phase Mg-Zn alloy. The addition of Al lowered the corrosion resistance of an anodised commercial purity Mg-Al single-phase alloy, whereas the same addition was found to be beneficial to the corrosion resistance of an anodised high purity Mg-Al single-phase alloy. Heat-treatment made the substrate Mg-Al and Mg-Zn alloys more uniform and hence improved the corrosion resistance of the alloys after anodisation. The detrimental effect of iron impurity on corrosion performance of the unanodised substrate single-phase magnesium alloys was inherited by the anodised alloys. The corrosion resistance of the anodised Mg alloys was found to be closely correlated with the corrosion performance of the unanodised as-cast Mg alloys. (c) 2005 Elsevier B.V. All rights reserved.

Coal ash conversion into effective adsorbents for removal of heavy metals and dyes from wastewater

Fly ash was modified by hydrothermal treatment using NaOH solutions under various conditions for zeolite synthesis. The XRD patterns are presented. The results indicated that the samples obtained after treatment are much different. The XRD profiles revealed a number of new reflexes, suggesting a phase transformation probably occurred. Both heat treatment and chemical treatment increased the surface area and pore volume. It was found that zeolite P would be formed at the conditions of higher NaOH concentration and temperature. The treated fly ash was tested for adsorption of heavy metal ions and dyes in aqueous solution. It was shown that fly ash and the modified forms could effectively absorb heavy metals and methylene blue but not effectively adsorb rhodamine B. Modifying fly ash with NaOH solution would significantly enhance the adsorption capacity depending on the treatment temperature, time, and base concentration. The adsorption capacity of methylene blue would increases with pH of the dye solution and the sorption capacity of FA-NaOH could reach 5 x 10(-5) mol/g. The adsorption isotherm could be described by the Langmuir and Freundlich isotherm equations. Removal of copper and nickel ions could also be achieved on those treated fly ash. The removal efficiency for copper and nickel ions could be from 30% to 90% depending on the initial concentrations. The increase in adsorption temperature will enhance the adsorption efficiency for both heavy metals. The pseudo second-order kinetics would be better for fitting the dynamic adsorption of Cu and Ni ions. (c) 2005 Elsevier B.V. All rights reserved.

Postharvest characteristics and handling of litchi fruit - an overview

Litchi ( Litchi chinensis Sonn.) is a tropical to subtropical crop that originated in South-East Asia. Litchi fruit are prized on the world market for their flavour, semi-translucent white aril and attractive red skin. Litchi is now grown commercially in many countries and production in Australia, China, Israel, South Africa and Thailand has expanded markedly in recent years. Increased production has made significant contributions to economic development in these countries, especially those in South-East Asia. Non-climacteric litchi fruit are harvested at their visual and organoleptic optimum. They are highly perishable and, consequently, have a short life that limits marketability and potential expansion of demand. Pericarp browning and pathological decay are common and important defects of harvested litchi fruit. Postharvest technologies have been developed to reduce these defects. These technologies involve cooling and heating the fruit, use of various packages and packaging materials and the application of fungicides and other chemicals. Through the use of fungicides and refrigeration, litchi fruit have a storage life of about 30 days. However, when they are removed from storage, their shelf life at ambient temperature is very short due to pericarp browning and fruit rotting. Low temperature acclimation or use of chitsoan as a coating can extend the shelf life. Sulfur dioxide fumigation effectively reduces pericarp browning, but approval from Europe, Australia and Japan for this chemical is likely to be withdrawn due to concerns over sulfur residues in fumigated fruit. Thus, sulfur-free postharvest treatments that maintain fruit skin colour are increasingly important. Alternatives to SO2 fumigation for control of pericarp browning and fruit rotting are pre-storage pathogen management, anoxia treatment, and dipping in 2% hydrogen chloride solution for 6-8 min following storage at 0 degrees C. Insect disinfestation has become increasingly important for the expansion of export markets because of quarantine issues associated with some fruit fly species. Thus, effective disinfestation protocols need to be developed. Heat treatment has shown promise as a quarantine technology, but it injures pericarp tissue and results in skin browning. However, heat treatment can be combined with an acid dip treatment that inhibits browning. Therefore, the primary aim of postharvest litchi research remains the achievement of highly coloured fruit which is free of pests and disease. Future research should focus on disease control before harvest, combined acid and heat treatments after harvest and careful temperature management during storage and transport.

Toxinology in Australia's colonial era: A chronology and perspective of human envenomation in 19th century Australia

The medical management of those envenomed by snakes, spiders and poisonous fish in Australia featured extensively in the writings 19th century doctors, expeditioners and anthropologists. Against the background of this introduced medical doctrine there already existed an extensive tradition of Aboriginal medical lore; techniques of heat treatment, suction, incision and the application of plant-derived pharmacological substances featured extensively in the management of envenomed victims. The application of a hair-string or grass-string ligature, suctioning of the bite-site and incision were practised in a variety of combinations. Such evolved independently of and pre-dated such practices, which were promoted extensively by immigrant European doctors in the late 19th century. Pacific scientific toxinology began in the 17th century with Don Diego de Prado y Tovar's 1606 account of ciguatera. By the end of the 19th century more than 30 papers and books had defined the natural history of Australian elapid poisoning. The medical management of snakebite in Australia was the focus of great controversy from 1860 to 1900. Dogmatic claims of the supposed antidote efficacy of intravenous ammonia by Professor G.B. Halford, and that of strychnine by Dr. Augustus Mueller, claimed mainstream medical attention. This era of potential iatrogenic disaster and dogma was brought to a conclusion by the objective experiments of Joseph Lauterer and Thomas Lane Bancroft in 1890 in Brisbane; and by those of C.J. Martin (from 1893) and Frank Tidswell (from 1898), both of Sydney. The modern era of Australian toxinology developed as a direct consequence of Calmette's discovery, in Paris in 1894, of immune serum, which was protective against snakebite. We review the key contributors and discoveries of toxinology in colonial Australia.

Development and evaluation of a non-destructive adhesion test

The object of this work was to further develop the idea introduced by Muaddi et al (1981) which enables some of the disadvantages of earlier destructive adhesion test methods to be overcome. The test is non-destructive in nature but it does need to be calibrated against a destructive method. Adhesion is determined by measuring the effect of plating on internal friction. This is achieved by determining the damping of vibrations of a resonating specimen before and after plating. The level of adhesion was considered by the above authors to influence the degree of damping. In the major portion of the research work the electrodeposited metal was Watt's nickel, which is ductile in nature and is therefore suitable for peel adhesion testing. The base metals chosen were aluminium alloys S1C and HE9 as it is relatively easy to produce varying levels of adhesion between the substrate and electrodeposited coating by choosing the appropriate process sequence. S1C alloy is the commercially pure aluminium and was used to produce good adhesion. HE9 aluminium alloy is a more difficult to plate alloy and was chosen to produce poorer adhesion. The "Modal Testing" method used for studying vibrations was investigated as a possible means of evaluating adhesion but was not successful and so research was concentrated on the "Q" meter. The method based on the use of a "Q" meter involves the principle of exciting vibrations in a sample, interrupting the driving signal and counting the number of oscillations of the freely decaying vibrations between two known preselected amplitudes of oscillations. It was not possible to reconstruct a working instrument using Muaddi's thesis (1982) as it had either a serious error or the information was incomplete. Hence a modified "Q" meter had to be designed and constructed but it was then difficult to resonate non-magnetic materials, such as aluminium, therefore, a comparison before and after plating could not be made. A new "Q" meter was then developed based on an Impulse Technique. A regulated miniature hammer was used to excite the test piece at the fundamental mode instead of an electronic hammer and test pieces were supported at the two predetermined nodal points using nylon threads. This instrument developed was not very successful at detecting changes due to good and poor pretreatments given before plating, however, it was more sensitive to changes at the surface such as room temperature oxidation. Statistical analysis of test results from untreated aluminium alloys show that the instrument is not always consistent, the variation was even bigger when readings were taken on different days. Although aluminium is said to form protective oxides at room temperature there was evidence that the aluminium surface changes continuously due to film formation, growth and breakdown. Nickel plated and zinc alloy immersion coated samples also showed variation in Q with time. In order to prove that the variations in Q were mainly due to surface oxidation, aluminium samples were lacquered and anodised Such treatments enveloped the active surfaces reacting with the environment and the Q variation with time was almost eliminated especially after hard anodising. This instrument detected major differences between different untreated aluminium substrates.Also Q values decreased progressively as coating thicknesses were increased. This instrument was also able to detect changes in Q due to heat-treatment of aluminium alloys.

Valence-tautomeric RbMnFe Prussian blue analogues:composition and time stability investigation

Three different stoichiometric forms of RbMn[Fe(CN) ]y·zHO [x = 0.96, y = 0.98, z = 0.75 (1); x = 0.94, y = 0.88, z = 2.17 (2); x = 0.61, y = 0.86, z = 2.71 (3)] Prussian blue analogues were synthesized and investigated by magnetic, calorimetric, Raman spectroscopic, X-ray diffraction, and Fe Mössbauer spectroscopic methods. Compounds 1 and 2 show a hysteresis loop between the high-temperature (HT) Fe(S = 1/2)-CN-Mn(S = 5/2) and the low-temperature (LT) Fe(S = 0)-CN-Mn(S = 2) forms of 61 and 135 K width centered at 273 and 215 K, respectively, whereas the third compound remains in the HT phase down to 5 K. The splitting of the quadrupolar doublets in the Fe Mössbauer spectra reveal the electron-transfer-active centers. Refinement of the X-ray powder diffraction profiles shows that electron-transfer-active materials have the majority of the Rb ions on only one of the two possible interstitial sites, whereas nonelectron-transfer-active materials have the Rb ions equally distributed. Moreover, the stability of the compounds with time and following heat treatment is also discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 2009.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.