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.

A critical review of the stress corrosion cracking (SCC) of magnesium alloys

This review aims to provide a foundation for the safe and effective use of magnesium (Mg) alloys, including practical guidelines for the service use of Mg alloys in the atmosphere and/or in contact with aqueous solutions. This is to provide support for the rapidly increasing use of Mg in industrial applications, particularly in the automobile industry. These guidelines should be firmly based on a critical analysis of our knowledge of SCC based on (1) service experience, (2) laboratory testing and (3) understanding of the mechanism of SCC, as well as based on an understanding of the Mg corrosion mechanism.

Hydrothermal Synthesis of Layered Double Hydroxides (LDHs) from Mixed MgO and Al2O3: LDH Formation Mechanism

The formation of MgA1 layered double hydroxide (LDH) from physically mixed MgO and Al2O3 oxides upon hydrothermal treatment has been extensively investigated, and a formation mechanism has been proposed. We observed that the formation of LDH from the oxide mixture occurs upon heating at 110 degreesC. In general, LDH is the major component while the minor phases are mainly determined by the initial pH of the oxide suspension as well as the MgO/Al2O3 ratio. The neutrality in the initial suspension results in a minor Mg(OH)(2) as the impure phase, while the alkalinity in the suspension keeps some MgO unreacted throughout the whole hydrothermal treatment. We suggest that MgO and Al2O3 be hydrated into Mg(OH)(2) and Al(OH)(3), respectively, in the initial stage for all samples. We further Suggest that in the neutral condition Mg(OH)2 be quickly dissociated to Mg2+ and OH- which then deposit on the surface of Al(OH)(3)/Al2O3 to form a M-Al pre-LDH material. Al(OH)(4)(-), ionized from Al(OH)(3) in the basic solution, deposits on the surface of Mg(OH)(2)/MgO to result in a similar MgAl pre-LDH material. Such a pre-LDH material is then well crystallized upon continuous heating via the diffusion of metal ions in the solid lattice. Such a dissociation-deposition-diffusion mechanism via two pathways has been supported by the phase composition, morphological features of crystallites, and [Mg]/[Al] ratios on the crystallite surface. and presumably applied to the general formation of LDHs with various synthetic methods. Such as coprecipitation, homogeneous preparation, and reconstruction.

Anodizing treatments for magnesium alloys and their effecton corrosion resistance in various environments

This paper reviews various aspects of anodizing of magnesium alloys, such as the basics, processes, properties and applications. It systematically summarises the existing fundamental studies and technical developments of anodizing of magnesium alloys, and concludes that new anodizing processes based on electrolytic plasma anodizing that convert the surface of a magnesium alloy into a hard ceramic coating in an electrolytic bath using high energy electric discharges can offer improved wear and corrosion resistance. These new anodized coatings are often claimed to perform better than the traditional ones obtained through older anodizing processes, such as DOW17 or HAE. The new anodizing techniques are chromate free and hence environment friendly. It is expected that more cost-effective, environment-friendly and non-toxic anodizing techniques will be developed and applied to magnesium alloy components in the future.

New solid bases for biodiesel synthesis

Biodiesel is a promising non-toxic and biodegradable renewable fuel, synthesized by the homogeneous base-catalyzed transesterification of vegetable oils or animal fats with methanol or ethanol. Removal of the base, typically Na or K alkoxide, after reaction is a major problem since aqueous quenching results in stable emulsions and saponification. The use of a solid base catalyst offers several process advantages including the elimination of a quenching step (and associated basic water waste) to isolate the products, and the opportunity to operate in a continuous process. The synthesis and characterization of a series of Li-doped CaO and Mg-Al hydrotalcite solid base catalysts were presented and their physicochemical properties were correlated with their activity in biodiesel synthesis. Both catalysts were effective solid bases for the transesterification of triglycerides to the methyl ester, with catalyst activity related to the electronic properties of Li and Mg dopants. This is an abstract of a paper presented at the 230th ACS National Meeting (Washington, DC 8/28/2005-9/1/2005).

Designer catalysts for biodiesel synthesis

The combination of dwindling oil reserves and growing concerns over carbon dioxide emissions and associated climate change is driving the urgent development of clean, sustainable energy supplies. Biodiesel is a non-toxic and biodegradable fuel, with the potential for closed CO2 cycles and thus vastly reduced carbon footprints compared with petroleum. However, current manufacturing routes employing soluble catalysts are very energy inefficient, with their removal necessitating an energy intensive separation to purify biodiesel, which in turn produces copious amounts of contaminated aqueous waste. The introduction of non-food based feedstocks and technical advances in heterogeneous catalyst and reactor design are required to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century. Here we report on the development of tuneable solid acid and bases for biodiesel synthesis, which offer several process advantages by eliminating the quenching step and allowing operation in a continuous reactor. Significant progress has been made towards developing tuneable solid base catalysts for biodiesel synthesis, including Li/CaO [1], Mg-Al hydrotalcites [2] and calcined dolomite [3] which exhibit excellent activity for triglyceride transesterification. However, the effects of solid base strength on catalytic activity in biodiesel synthesis remains poorly understood, hampering material optimisation and commercial exploitation. To improve our understanding of factors influencing solid base catalysts for biodiesel synthesis, we have applied a simple spectroscopic method for the quantitative determination of surface basicity which is independent of adsorption probes. Such measurements reveal how the morphology and basicity of MgO nanocrystals correlate with their biodiesel synthesis activity [4]. While diverse solid acids and bases have been investigated for TAG transesterification, the micro and mesoporous nature of catalyst systems investigated to date are not optimal for the diffusion of bulky and viscous C16-C18 TAGs typical of plant oils. The final part of this presentation will address the benefits of designing porous networks comprising interconnected hierarchical macroporous and mesoporous channels (Figure 1) to enhance mass-transport properties of viscous plant oils during biodiesel synthesis [5]. References: [1] R.S. Watkins, A.F. Lee, K. Wilson, Green Chem., 2004, 6, 335. [2]D.G. Cantrell, L.J. Gillie, A.F. Lee and K. Wilson, Appl. Catal. A, 2005, 287,183. [3] C. Hardacre, A.F. Lee, J.M. Montero, L. Shellard, K.Wilson, Green Chem., 2008, 10, 654. [4] J.M. Montero, P.L. Gai, K. Wilson, A.F. Lee, Green Chem., 2009, 11, 265. [5] J. Dhainaut, J.-P. Dacquin, A.F. Lee, K. Wilson, Green Chem., 2010, 12, 296.

Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites:fact or fiction?

Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.

Derivation of base-line geochemistry, petrography, and isotopic data for the host rocks to the Lucky Strike deposit and comparison with data from other alteration zones, Buchans Mining Camp, Newfoundland

The Buchans ore bodies of central Newfoundland represent some of the highest grade VMS deposits ever mined. These Kuroko-type deposits are also known for the well developed and preserved nature of the mechanically transported deposits. The deposits are hosted in Cambro-Ordovician, dominantly calc-alkaline, bimodal volcanic and epiclastic sequences of the Notre Dame Subzone, Newfoundland Appalachians. Stratigraphic relationships in this zone are complicated by extensively developed, brittledominated Silurian thrust faulting. Hydrothermal alteration of host rocks is a common feature of nearly all VMS deposits, and the recognition of these zones has been a key exploration tool. Alteration of host rocks has long been described to be spatially associated with the Buchans ore bodies, most notably with the larger in-situ deposits. This report represents a base-line study in which a complete documentation of the geochemical variance, in terms of both primary (igneous) and alteration effects, is presented from altered volcanic rocks in the vicinity of the Lucky Strike deposit (LSZ), the largest in-situ deposit in the Buchans camp. Packages of altered rocks also occur away from the immediate mining areas and constitute new targets for exploration. These zones, identified mostly by recent and previous drilling, represent untested targets and include the Powerhouse (PHZ), Woodmans Brook (WBZ) and Airport (APZ) alteration zones, as well as the Middle Branch alteration zone (MBZ), which represents a more distal alteration facies related to Buchans ore-formation. Data from each of these zones were compared to those from the LSZ in order to evaluate their relative propectivity. Derived litho geochemical data served two functions: (i) to define primary (igneous) trends and (ii) secondary alteration trends. Primary trends were established using immobile, or conservative, elements (i. e., HFSE, REE, Th, Ti0₂, Al₂0₃, P₂0₅). From these, altered volcanic rocks were interpreted in terms of composition (e.g., basalt - rhyodacite) and magmatic affinity (e.g., calc-alkaline vs. tholeiitic). The information suggests that bimodality is a common feature of all zones, with most rocks plotting as either basalt/andesite or dacite (or rhyodacite); andesitic senso stricto compositions are rare. Magmatic affinities are more varied and complex, but indicate that all units are arc volcanic sequences. Rocks from the LSZ/MBZ represent a transitional to calc-alkalic sequence, however, a slight shift in key geochemical discriminants occurs between the foot-wall to the hanging-wall. Specifically, mafic and felsic lavas of the foot-wall are of transitional (or mildly calc-alkaline) affinity whereas the hanging-wall rocks are relatively more strongly calc-alkaline as indicated by enriched LREE/HREE and higher ZrN, NbN and other ratios in the latter. The geochemical variations also serve as a means to separate the units (at least the felsic rocks) into hanging-wall and foot-wall sequences, therefore providing a valuable exploration tool. Volcanic rocks from the WBZ/PHZ (and probably the APZ) are more typical of tholeiitic to transitional suites, yielding flatter mantlenormalized REE patterns and lower ZrN ratios. Thus, the relationships between the immediate mining area (represented by LSZ/MBZ) and the Buchans East (PHZ/WBZ) and the APZ are uncertain. Host rocks for all zones consist of mafic to felsic volcanic rocks, though the proportion of pyroclastic and epiclastic rocks, is greatest at the LSZ. Phenocryst assemblages and textures are common in all zones, with minor exceptions, and are not useful for discrimination purposes. Felsic rocks from all zones are dominated by sericiteclay+/- silica alteration, whereas mafic rocks are dominated by chlorite- quartz- sericite alteration. Pyrite is ubiquitous in all moderately altered rocks and minor associated base metal sulphides occur locally. The exception is at Lucky Strike, where stockwork quartzveining contains abundant base-metal mineralization and barite. Rocks completely comprised of chlorite (chloritite) also occur in the LSZ foot-wall. In addition, K-feldspar alteration occurs in felsic volcanic rocks at the MBZ associated with Zn-Pb-Ba and, notably, without chlorite. This zone represents a peripheral, but proximal, zone of alteration induced by lower temperature hydrothermal fluids, presumably with little influence from seawater. Alteration geochemistry was interpreted from raw data as well as from mass balanced (recalculated) data derived from immobile element pairs. The data from the LSZ/MBZ indicate a range in the degree of alteration from only minor to severe modification of precursor compositions. Ba tends to show a strong positive correlation with K₂0, although most Ba occurs as barite. With respect to mass changes, Al₂0₃, Ti0₂ and P₂0₅ were shown to be immobile. Nearly all rocks display mass loss of Na₂O, CaO, and Sr reflecting feldspar destruction. These trends are usually mirrored by K₂0-Rb and MgO addition, indicating sericitic and chloritic alteration, respectively. More substantial gains ofK₂0 often occur in rocks with K-feldspar alteration, whereas a few samples also displayed excessive MgO enrichment and represent chloritites. Fe₂0₃ indicates both chlorite and sulphide formation. Si0₂ addition is almost always the case for the altered mafic rocks as silica often infills amygdules and replaces the finer tuffaceous material. The felsic rocks display more variability in Si0₂. Silicic, sericitic and chloritic alteration trends were observed from the other zones, but not K-feldspar, chloritite, or barite. Microprobe analysis of chlorites, sericites and carbonates indicate: (i) sericites from all zones are defined as muscovite and are not phengitic; (ii) at the LSZ, chlorites ranged from Fe-Mg chlorites (pycnochlorite) to Mg-rich chlorite (penninite), with the latter occurring in the stockwork zone and more proximal alteration facies; (iii) chlorites from the WBZ were typical of those from the more distal alteration facies of the LSZ, plotting as ripidolite to pycnochlorite; (iv) conversely, chlorite from the PHZ plot with Mg-Al-rich compositions (chlinochlore to penninite); and (v) carbonate species from each zone are also varied, with calcite occurring in each zone, in addition to dolomite and ankerite in the PHZ and WBZ, respectively. Lead isotope ratios for galena separates from the different various zones, when combined with data from older studies, tend to cluster into four distinctive fields. Overall, the data plot on a broad mixing line and indicate evolution in a relatively low-μ environment. Data from sulphide stringers in altered MBZ rocks, as well as from clastic sulphides (Sandfill prospect), plot in the Buchans ore field, as do the data for galena from altered rocks in the APZ. Samples from the Buchans East area are even more primitive than the Buchans ores, with lead from the PHZ plotting with the Connel Option prospect and data from the WBZ matching that of the Skidder prospect. A sample from a newly discovered debris flow-type sulphide occurrence (Middle Branch East) yields lead isotope ratios that are slightly more radiogenic than Buchans and plot with the Mary March alteration zone. Data within each cluster are interpreted to represent derivation from individual hydrothermal systems in which metals were derived from a common source.

Geochemical composition of ODP Site 210-1276 shales

During Ocean Drilling Program Leg 210, a greatly expanded sedimentary sequence of continuous Cretaceous black shales was recovered at Site 1276. This section corresponds to the Hatteras Formation, which has been documented widely in the North Atlantic Ocean. The cored sequence extends from the lowermost Albian, or possibly uppermost Aptian, to the Cenomanian/Turonian boundary and is characterized by numerous gravity-flow deposits and sporadic, finely laminated black shales. The sequence also includes several sedimentary intervals with high total organic carbon (TOC) contents, in several instances of probable marine origin that may record oceanic anoxic events (OAE). These layers might correspond to the Cenomanian-Turonian OAE 2; the mid-Cenomanian event; and OAE 1b, 1c, and 1d in the Albian. In addition, another interval with geochemical characteristics similar to OAE-type layers was recognized in the Albian, although it does not correspond to any of the known OAEs. This study investigates the origin of the organic matter contained within these black shale intervals using TOC and CaCO3 contents, Corg/Ntot ratios, organic carbon and nitrogen isotopes, trace metal composition, and rock-eval analyses. Most of these black shale intervals, especially OAE 2 and 1b, are characterized by low 15N values (<0) commonly observed in mid-Cretaceous black shales, which seem to reflect the presence of an altered nitrogen cycle with rates of nitrogen fixation significantly higher than in the modern ocean.

Mineralogy, geochemistry and elemental ratios of ODP Core 171B-1049C-8X

Inorganic geochemistry and mineralogy of Core 171B-1049C-8X, containing a Cretaceous/Tertiary boundary section, was investigated by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The ages of samples analyzed stretched from the latest Maastrichtian into the Danian. XRD measurements were made using the peak height method. A reduction in low-magnesium calcite and an increase in quartz were found above the spherule layer. Substantial amounts of dolomite were noted just above the spherule layer. XRF analyses were performed using the RHSMALL program to measure the abundance of major and minor elements. Replicate analyses for each technique were performed to assess the precision of the results. The section above the spherule bed was found to be characterized by peaks in many elements, including Si, Al, Fe, and Mg, as well as the following elemental ratios: Fe/Al, Ni/Al, Zr/Rb, and Rb/Sr'. Above the spherule bed, there were significant reductions in Ca, Sr/Ca, Ti/Al, K/Al, Rb/Al, Cr/Al, Ba/Al, biogenic Ba, and excess P.

Aproximación al clítico 的 de en chino

Debido a las características intrínsecas de la lengua china, los clíticos juegan un papel imprescindible en la estructura sintáctica del idioma. Sin ellos, las oraciones no llegan a construirse, ya que son estos, entre otros recursos, los que cargan las informaciones gramaticales; es más, cada clítico en chino ocupa un hueco en la gramática, por lo que es difícil remplazarlos sin cambiar el sentido de la oración. De todos los clíticos, la palabra «的» es la que se presenta con mayor frecuencia. Esta palabra, como muchas otras “palabras vacías”, desempeña diversas funciones gramaticales, por lo que constituye un punto de investigación muy interesante en la gramática china. Desde los años 20 del siglo pasado, generaciones de eruditos se han dedicado a su estudio, entre otros, figuran Li Jinxi（黎锦熙), Gao Mingkai（高名凯),Chen Qiongzan（陈琼瓒), Fan Jiyan（范继淹）y Zhu Dexi（朱德熙). Un artículo de este último Sobre “的 (De)” ha provocado una amplia reacción y una profunda influencia en las investigaciones posteriores. A pesar de todo y hasta hoy en día, el uso de esta palabra sigue siendo un escollo tanto para los profesores de chino como para sus alumnos. Las ambigüedades que puede causar y la diferencia semántica y pragmática de su uso y desuso han sido un rompecabezas no sólo para los extranjeros, sino también para los nativos. En este artículo, intentaremos delimitar sus usos y analizar sus valores semánticos y pragmáticos.

Impacto de los Niveles de Tacrolimus en el Rechazo al Injerto y la Tasa de Filtración Glomerular en Pacientes con Trasplante Hepático realizado en la FCI-IC entre 2009 y 2014

Introducción: El tacrolimus es el medicamento de elección para evitar el rechazo al injerto hepático. Su dosis se ajusta a partir de los niveles séricos que se toman periódicamente para asegurar rango terapéutico. Además, niveles elevados se asocian con disfunción renal postrasplante. Sin embargo, no hay consenso frente a los niveles adecuados para pacientes con trasplante hepático. Objetivo: Determinar la relación entre los niveles de tacrolimus y la presencia de rechazo agudo al injerto hepático en pacientes con trasplante hepático realizado en la Fundación Cardioinfantil – Instituto de Cardiología (FCI-IC). Determinar la relación entre los niveles de tacrolimus y la TFG en pacientes con trasplante hepático realizado en la FCI-IC. Métodos: Estudio observacional tipo cohorte histórica en pacientes adultos con trasplante hepático realizado en la FCI-IC entre 2009-2014. Resultados: No se encontró una asociación estadísticamente significativa entre los niveles de tacrolimus y la presencia de rechazo agudo, en sus diferentes definiciones (OR=1,02, p=0,14 y OR=1,01, p=0,29) incluso al ajustar por otras covariables (OR=1,03, p=0,10 y OR=1,02, p=0,25). No fue posible corroborar el diagnóstico con biopsia porque no todos la tenían. Si bien la relación entre los niveles de tacrolimus y la TFG fue estadísticamente significativa (p≤0,001), tiene bajo impacto clínico, pues la TFG disminuyó menos de un punto por cada incremento en 1 ng/ml en los niveles de tacrolimus. Conclusiones: Se necesitan más estudios para establecer la relación entre la exposición a tacrolimus y estos desenlaces para definir si es seguro disminuir su dosis con el fin de reducir los eventos adversos.

EIS study of Ti-23Ta alloy in artificial saliva

Although titanium and Ti-6Al-4V alloy have been widely used as dental materials, possible undesirable effects such as cytotoxic reactions and neurological disorder due to metal release led to the development of more corrosion resistant and V and Al free titanium alloys, containing Nb, Zr, Mo and Ta atoxic elements. Fluoride containing products used in the prevention of plaque formation and dental caries can affect the stability of the passive oxide films formed on the Ti alloys. In this work, the corrosion behaviour of the new Ti-23Ta alloy has been evaluated in artificial saliva of different pH and fluoride concentration using electrochemical impedance spectroscopy. Electrochemical impedance spectroscopy study showed that the oxide film formed on the alloy in artificial saliva consists of an inner compact film and an outer porous layer. The corrosion resistance of Ti-23Ta alloy which is reduced by increasing F concentration or decreasing pH is related to the resistance of the inner compact layer. The presence of fluoride and low pH of the saliva enhance the porosity of the oxide film and its dissolution.

Corrosion behavior of Ti-xNb-13Zr alloys in Ringer`s solution

Ti-6Al-4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V-free alloys and both V- and Al-free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti-13Nb-13Zr alloy is promising due to its better biomechanical compatibility than Ti-6Al-4V. In this work, the corrosion behavior of Ti, Ti-6Al-4V, and Ti-xNb-13Zr alloys (x=5, 13, and 20) was evaluated in Ringer`s solution (pH 7.5) at 37 degrees C through open-circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10(-7) A/cm(2)) and high impedance values (in the order of 10(5) Omega cm(2) at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti-xNb-13Zr alloys were more corrosion resistant than both Ti and Ti-6Al-4V in Ringer`s solution.

Avalia????o da integra????o do programa de erradica????o do trabalho infantil ao programa bolsa fam??lia

O artigo descreve e avalia o novo modelo do Programa de Erradica????o do Trabalho Infantil (PETI) integrado ao Programa Bolsa Fam??lia (PBF). Mostra que o desenho para implementar a integra????o contribuiu para racionaliza????o e aprimoramento dos processos de gest??o do PBF e PETI: pelo Cadastro ??nico, reduziu gastos administrativos, facilitou monitoramento e avalia????o e contribuiu para melhor aplica????o dos recursos do PETI; pelo SISPETI, tornou poss??vel acompanhar a oferta das a????es socioeducativas e de conviv??ncia pelos munic??pios. Argumenta que, como as causas do trabalho infantil v??o al??m da insufici??ncia de renda, ao enfatizar o crit??rio da renda e equalizar o tratamento das fam??lias que possuem crian??as e adolescentes em situa????o de trabalho infantil e as que n??o registram essa pr??tica, o modelo de integra????o adotado pode ter tornado fr??geis os incentivos ?? retirada das crian??as e adolescentes do trabalho infantil. Conseq??entemente, pode ter enfraquecido a pol??tica de combate ao trabalho infantil.