Use of a new enrichment nanosorbent for speciation of mercury by FI-CV-ICP-MS

Mercury is one of the most toxic environmental pollutants and its effects on human and ecosystem health are well known. All mercury species are toxic, with organic mercury compounds generally being more toxic than inorganic species. Chromatography techniques (GC, HPLC) coupled to element specific detectors, are able to separate mercury species in order to elucidate mercury transformation and transport processes where the determination of all mercury species is desirable. However, in practice, especially in sampling campaigns for sea water analysis where a large number of samples are collected over a longer period of time, a combination of methods is usually applied to accurately determine the most toxic mercury species. These include non-chromatographic methods based on the different chemical and/or physical behavior of the mercury species. These non-chromatographic methods can be less time consuming, more cost effective and available, and present competitive limits of detection. Especially when mercury could vapor (CV) generation technique is employed, which reduces salt effect on the analytical signal and improve the sensibility. Among non-chromatographic methods, solid phase extraction and microextraction (SPE and SPME) which is becoming increasingly popular for sample preparation in organic analysis, found its way to speciation analysis of organometals. SPE/SPME is the most popular sample preconcentration method for its simplicity, high enrichment factor, low or no consumption of organic solvents and feasibly to be automated. On the other hand, the exploration of new materials, especially nanometer sized materials, as the support phase is another active research area in SPE/SPME for mercury determination. The use of nanoparticles leads to higher extraction capacity/efficiency and rapid dynamics of extraction originated from the higher surface area to volume ratio and short diffusion route. In this work, a new enrichment nanosorbent functionalized with 1,5 bis (2-pyridyl) methylene thiocarbohidrazide was synthesized and characterized. From the study of its adsorption capacity toward metal ions, Hg2+ was observed to be one of the most retained 173.1 µmol g-1 at pH 5. Thus, a flow injection solid phase extraction and cold vapor generation method for its determination and speciation based on the use of this new chelating nanosorbent was optimized. The method developed has showed to be useful for the automatic pre-concentration and sequential speciation of mercury and methylmercury in environmental and biological samples. The system was based on chelating retention of the analytes onto a mini-column filled with the new nanosorbent and their sequential elution by using two different eluents, 0.2 % HCl for CH3Hg+ and 0.1 % thiourea in 0.5 % HCl for Hg2+. The determination was performed using inductively coupled plasma mass spectrometry. Under the optimum conditions and 120 s preconcentration time, the enrichment factors were 4.7 and 11.0; the detection limits (3σ) were 0.002 and 0.004 µg L-1; the determination limits (10σ) were 0.011 and 0.024 µg L-1; and the precisions (calculated for 10 replicate determinations at a 2 µg L-1 standard of both species) were 2.8 and 2.6 % (RSD); for CH3Hg+ and Hg2+, respectively. Linear calibration graphs were obtained for both species from the determination limits to at least 70 µg L-1. For the quality control of the analytical performance and the validation of the newly developed method, the analysis of two certified samples, LGC 6016 estuarine water and SRM 2976 mussel tissue were addressed. The results showed good agreement with the certified values. The method was successfully applied to the speciation of mercury in sea-water samples collected in the Málaga Bay.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Development of Bioglass/PEEK Composite Coating by Cold Gas Spray for Orthopedic Implants

Cold gas spray (CGS) technology has allowed the development of biofunctional coatings composed of 45S5 and polyetheretherketone (PEEK). The combination of a bioactive glass material embedded in a polymeric matrix makes this composite an interesting material for orthopedic applications since this composite meets the biomechanical and biological requirements of an implant. In the present study, blends of bioactive glass 45S5 and PEEK powder with different granulometry and 45S5/PEEK ratio have been prepared. These mixtures of powders have been deposited onto PEEK substrates by CGS with the goal of incorporating a bioactive additive to the biocompatible polymer, which can improve the bone-implant interaction of PEEK. The deposition efficiency (DE) of the coatings has been evaluated, and from the results obtained, it was possible to conclude that DE is significantly affected by the granulometry and by the 45S5/PEEK ratio of the blends. By scanning electron microscopy (SEM) inspection, it was observed that the use of blends with high 45S5/PEEK ratio lead to the deposition of coatings with high content of 45S5. Finally, the friction behavior of the coatings was analyzed performing ball-on-disk tests and these experiments showed that the presence of glass particles has a beneficial role in the wear resistance

Perspective Chapter: Hydroxyapatite - Surface Functionalization to Prevent Bacterial Colonization

Microbial colonization is one of the main causes of implant loosening and rejection. Pathogenic contamination and the subsequent biofilm formation reduce the implant’s chance of survival and can be life-threatening to a patient. Among the many strategies employed to reduce the infection probability of bioceramics, surface functionalization plays a key role. This chapter is dedicated to describing the different strategies available to prevent bacterial colonization and the proliferation of hydroxyapatite-coated implants. Moreover, the factors intervening in the bacteria-implant interaction will be described, detailing the mechanisms involved during the contact, adhesion, and proliferation of bacteria. Finally, the characterization methods will be discussed, emphasizing the bioactivity and antibacterial assays

Rheological behaviour of submicron mullite-carbon nanofiber suspensions for Atmospheric Plasma Spraying coatings

Mullite is widely used as a structural material for applications like thermal and environmental barriers coatings. For some of these applications, thermal spray is a suitable technique due to its fast production time and versatility. This makes mullite a very interesting coating material for thermal spray industry. In the present work, the viability to produce coatings by thermal spray using mullite-CNFs agglomerated powders is analyzed. The stability of aqueous mullite and mullite-CNFs suspensions was studied in terms of zeta potential and rheological behaviour of concentrated slurries. Slurries were optimized in terms of dispersant concentration and solid content. The optimized suspensions were used for the granules preparation by spray drying technology. The obtained granules were characterized through the determination of particle size distribution and shape factor by field emission scanning electron microscopy and laser scattering. These granules were used to form the coatings by Atmospheric Plasma Spraying which were characterized by evaluating the composition, structure, shape, and thickness

Sequential determination of heavy metals in environmental water samples by flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry

The toxicity of “heavy metals” has been well recognized for a long time. Often the non-specific term “heavy metals” is used for three of the metals, cadmium, mercury and lead. These have large bioconcentration factors in marine organism, are highly toxic and, unlike many of the transition elements have no known natural biological functions. For these reasons these metals generate the greatest concern for the general public and therefore also for environmental agencies in the majority of states. The monitoring and control of these trace elements in the environment requires powerful analytical methods to accurately characterize their abundance and to reach reliable conclusions. In this work, an inductively coupled plasma mass spectrometry (ICP-MS) method has been developed for the sequential determination of Pb, Cd and Hg in natural waters, including sea-water, using an on-line preconcentration flow injection chemical vapour generation system (FI-CVG). It is difficult to simultaneously determine these elements by CVG, because their conditions of CVG are different. Thus, the system was based on the use of two minicolumns packed with 1-(di-2-pyridyl)methylene thiocarbonohydrazide chelating resin which were placed in two injection valves of a simple flow manifold to be loaded simultaneously. A third valve was arranged to select the reagent for the selective vapour generation of the analytes and, thus make possible the sequential determination of the three metals. By using this device, diverse advantages are attained: increase of the sensitivity and reduction of the interferences by the preconcentration and the vapour generation. The detection limits achieved (3 min sample loading time) were: 9, 17 and 12 ngL-1 for Pb, Cd and Hg, respectively, with a sample throughput about 10.4 h-1. The accuracy of the proposed method was checked with three certified reference materials (CRMs): TMDA-54.4 fortified lake water, LGC6016 estuarine water and CASS-5 oceanic water and the results obtained were in good agreement with the certified values. The method was also applied to the determination of Pb, Cd and Hg in different sea-water samples from the Málaga Bay.Universidad de Málaga, Campus de Excelencia Internacional Andalucia Tec

Improving the Wear and Corrosion Resistance of Maraging Part Obtained by Cold Gas Spray Additive Manufacturing

The use of the cold gas spray (CGS) process as a metal additive manufacturing (MAM) technique for metallic part production has been deeply studied recently, mainly due to its advantages over other MAM techniques. CGS MAM is a high-productivity technique with a very low level of particle oxidation, microstructural changes, phase transformations, or deleterious residual thermal stresses in the part. The use of CGS MAM to produce maraging parts represents a gain for the industry by saving machining time and preventing raw material waste. Its wear resistance and corrosion behavior were evaluated in this work and were compared with cermet coatings deposited by high-velocity oxy-fuel (HVOF) on the CGS MAM maraging. This work presents the innovative and effective combination of different thermal spraying processes and materials to obtain MAM maraging parts with higher wear resistance, evaluating abrasion, sliding, and water erosion wear type

Comparison of Stellite coatings on low carbon steel produced by CGS and HVOF spraying

Stellite alloys are of great interest in industries due to a unique combination of high temperature mechanical strength, outstanding wear and corrosion resistance. Different thermal spraying processes are used for deposition of stellite alloys on industrial components. However, the investigations on the structure-property relationship of these alloys produced via different deposition process are limited. This study focuses on the microstructure, oxidation, and tribo-mechanical properties of Stellite 21 deposited by cold gas spraying (CGS) and high velocity oxy-fuel (HVOF) process on a low carbon steel substrate. The coating cross- section was characterized by SEM and optical microscopy. The coatings were further characterised by using nanoindentation, adhesion, and ball-on-disk wear tests. Moreover, XRD tests were run on the powder and the coatings to reveal possible phase transformation during spraying, as well as during wear and oxidation tests. The results showed no phase transformation in the as-sprayed CGS coating, besides higher values of porosity and oxide phase in the HVOF coating. However, an fcc-to-hcp phase transformation occurs at the surface layer of both types of coating during the ball-on-disk wear test. The presence of continuous oxide networks in HVOF coatings leads to delamination during the wear test. Overall, the CGS Stellite 21 coatings exhibit better performance than HVOF coatings in wear and oxidation tests

The influence of the powder characteristics on 316L stainless steel coatings sprayed by cold gas spray

Thermally sprayed 316L stainless steel coatings are commonly used on metallic structures due to their corrosion and wear resistance when compared to carbon steel. Cold Gas Spray (CGS) is a convenient thermal spray process to deposit 316L coatings, producing thick and very dense coatings, with almost no deleterious changes on the feedstock properties to the coating condition. The powder characteristics have influence on the microstructure of the coating, such as porosity and oxide contents, which alter its corrosion and wear behavior. CGS is an efficient technique to reduce the problems associated with material melting commonly found in other conventional thermal spray methods. In this work, different 316L powders, produced by different manufacturers, were deposited by CGS, applying the same equipment and parameters, with the objective to evaluate the relation between the powders' characteristics and coating properties. Their microstructure, adherence, hardness, as well as the performance on corrosion and wear testing were evaluated. The water atomized powders presented in general better results than gas atomized powders

FeAl and NbAl3 intermetallic- HVOF coatings: structure and properties

Transition metal aluminides in their coating form are currently being explored in terms of resistance to oxidation and mechanical behavior. This interest in transition metal aluminides is mainly due to the fact that their high Al content makes them attractive for high-temperature applications. This is also a reason to study their resistance to wear; they may be suitable for use in applications that produce a lot of wear in aggressive environments, thus replacing established coating materials. In this study, the microstructure, microhardness, and wear and oxidation performance of FeAl and NbAl3 coatings produced by highvelocity oxy-fuel spraying are evaluated with two main aims: (i) to compare these two coating systems¿a commonly studied aluminide (FeAl) and, NbAl3, an aluminide whose deposition by thermal spraying has not been attempted to date¿and (ii) to analyze the relationship between their microstructure, composition and properties, and so clarify their wear and oxidation mechanisms. In the present study, the higher hardness of niobium aluminide coatings did not correlate with a higher wear resistance and, finally, although pesting phenomena (disintegration in oxidizing environments) were already known of in bulk niobium aluminides, here their behavior in the coating form is examined. It was shown that such accelerated oxidation was inevitable with respect to the better resistance of FeAl, but further improvements are foreseen by addition of alloying elements in that alloy