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Henderson, R. G., Verougstraete, V., Anderson, K., Arbildua, J. J., Brock, T. O., Brouwers, T., et al. (2014). Inter-laboratory validation of bioaccessibility testing for metals. Regul. Toxicol. Pharmacol., 70(1), 170–181.
Abstract: Bioelution assays are fast, simple alternatives to in vivo testing. In this study, the intra- and inter-laboratory variability in bioaccessibility data generated by bioelution tests were evaluated in synthetic fluids relevant to oral, inhalation, and dermal exposure. Using one defined protocol, five laboratories measured metal release from cobalt oxide, cobalt powder, copper concentrate, Inconel alloy, leaded brass alloy, and nickel sulfate hexahydrate. Standard deviations of repeatability (S-r) and reproducibility (S-R) were used to evaluate the intra- and inter-laboratory variability, respectively. Examination of the s(R):s(r) ratios demonstrated that, while gastric and lysosomal fluids had reasonably good reproducibility, other fluids did not show as good concordance between laboratories. Relative standard deviation (RSD) analysis showed more favorable reproducibility outcomes for some data sets; overall results varied more between- than within-laboratories. RSD analysis of s(r) showed good within-laboratory variability for all conditions except some metals in interstitial fluid. In general, these findings indicate that absolute bioaccessibility results in some biological fluids may vary between different laboratories. However, for most applications, measures of relative bioaccessibility are needed, diminishing the requirement for high inter-laboratory reproducibility in absolute metal releases. The inter-laboratory exercise suggests that the degrees of freedom within the protocol need to be addressed. (C) 2014 Elsevier Inc. All rights reserved.
Keywords: Metals; Alloys; UVCBs; Classification; Bioelution; Bioaccessibility; Read-across; Inter-laboratory validation
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Martinez, C., Briones, F., Rojas, P., Aguilar, C., Guzman, D., & Ordonez, S. (2017). Microstructural and mechanical characterization of copper, nickel, and Cu-based alloys obtained by mechanical alloying and hot pressing. Mater. Lett., 209, 509–512.
Abstract: Mechanical alloying and uniaxial compaction were used to obtain configurations of: elemental powders of Cu and Ni; binary alloys (Cu-Ni and Cu-Zr); and a ternary alloy (Cu-Ni-Zr) under the same mechanical milling and hot pressing conditions. Microstructure and mechanical properties of these were investigated. According to XRD results, hot pressing process increases crystallite size and decreases microstrain in the compact samples, due to the release of crystalline defects without crystallization of amorphous alloys. The milled powder samples have a higher hardness than the unmilled samples, since crystal defects are incorporated into microstructural refinement during milling. The ternary alloy Cu-40Ni-10Zr had the highest hardness of all systems studied, reaching 689 HV0.5. Compression tests at 5% strain determined that Zr-containing samples (amorphous phase) become more fragile after processing, and have the lowest values of compressive strength. In contrast, Ni samples and Cu-Ni binary alloys are more resistant to compression. (
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Martinez, C., Briones, F., Rojas, P., Ordonez, S., Aguilar, C., & Guzman, D. (2017). Microstructure and Mechanical Properties of Copper, Nickel and Ternary Alloys Cu-Ni-Zr Obtained by Mechanical Alloying and Hot Pressing. MRS Adv., 2(50), 2831–2836.
Abstract: Elemental powders of Cu and Ni, binary alloys (Cu-Ni and Cu-Zr) and ternary alloy (Cu-Ni-Zr) obtained by mechanical alloying and uniaxial compaction hot microstructure and mechanical properties were investigated. The alloys studied were: pure Cu, pure Ni, binary alloys (Cu-Ni; Cu-Zr) and ternary alloys (Cu-Ni-Zr) under the same mechanical milling and hot pressing conditions. The samples were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM); the mechanical properties were studied by compression tests and hardness in Vickers scale (HV0.5) on polished surfaces at room temperature. According to XRD results, hot pressing process crystallite size increase and microstrain decreases in the compact samples due to the release of crystalline defects. The compacted samples have porosity of approximately 20%. The milling powder samples have a higher hardness than the unmilled samples, this because during milling crystal defects are incorporated together with the microstructural refinement. Ternary alloy is the one with the highest hardness of all systems studied, reaching 689 HV0.5. In compression tests determined a strain 5 %, Zr-containing samples become more fragile presenting the lowest values of compressive strength. In contrast, samples of Ni and Cu-Ni binary alloy are more resistant to compression.
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Shanmugaraj, K., Mangalaraja, R. V., Campos, C. H., Udayabhaskar, R., Singh, D. P., Vivas, L., et al. (2023). Cu-Ni bimetallic nanoparticles anchored on halloysite nanotubes for the environmental remediation. Surf. Interfaces, 41, 103257.
Abstract: Hereby, we report the synthesis of CuNi bimetallic nanoparticles (NPs)-decorated halloysite nanotubes (CuNi/ HNTs) for the catalytic reduction of 4-nitroaniline (4-NA) and rhodamine B (RhB) dye in an aqueous medium at room temperature. In this work, CuNi/HNTs composites with different wt% of CuNi NPs were synthesized and characterized by various techniques such as SEM, EDS, XRD, TEM and XPS. The TEM characterization confirmed that the CuNi bimetallic NPs (similar to 11 nm) were successfully anchored onto the outer surface of HNTs. Among the prepared catalysts, Cu0.75Ni0.25/HNTs catalyst displayed highest catalytic activity in the reduction of 4-NA to its corresponding amino derivative in the presence of NaBH4 with a maximum conversion efficiency of >99% and an apparent rate constant k(app) of 0.152 s(- 1) within 30 s of reaction time. Notably, even after 15 cycles of catalytic reduction of 4-NA and RhB, there was no apparent deactivation of the catalytic activity of the Cu0.75Ni0.25/HNTs catalyst, demonstrating the excellent catalytic reusability and stability. The presence of CuNi NPs with low Ni content enhanced the catalytic activity due to the synergetic effect. Moreover, the continuous flow fixed bed reactor designed with Cu0.75Ni0.25/HNTs catalyst exhibited the potential application for the reduction of 4-NA and RhB dye under mild reaction conditions. Furthermore, the present catalytic system could be applicable for the treatment of various wastewater effluents.
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Urrestarazu, P., Villavicencio, G., Opazo, M., Arbildua, J., Boreiko, C., Delbeke, K., et al. (2014). Migration protocol to estimate metal exposure from mouthing copper and tin alloy objects. Environ. Health, 13, 9 pp.
Abstract: Background: Low blood lead levels previously thought to pose no health risks may have an adverse impact on the cognitive development of children. This concern has given rise to new regulatory restrictions upon lead metal containing products intended for child use. However few reliable experimental testing methods to estimate exposure levels from these materials are available. Methods: The present work describes a migration test using a mimetic saliva fluid to estimate the chronic exposure of children to metals such as lead while mouthing metallic objects. The surrogate saliva medium was composed of: 150 mM NaCl, 0.16% porcine Mucin and 5 mM buffer MOPS, adjusted to pH 7.2. Alloys samples, in the form of polished metallic disc of known surface area, were subjected to an eight hours test. Results: Two whitemetal alloys Sn/Pb/Sb/Cu and three brass alloys Cu/Zn/Pb were tested using the saliva migration protocol. In the case of the whitemetal alloys, first order release kinetics resulting in the release of 0.03 and 0.51 μg lead/cm(2) after 8 hours of tests were observed, for lead contents of 0.05-0.07% and 5.5%, respectively. Brasses exhibited linear incremental release rates of 0.043, 0.175 and 0.243 μg lead/cm(2)h for lead contents of 0.1-0.2%, 1.7-2.2% and 3.1-3.5%, respectively. The linear regression analysis of lead release rates relative to Pb content in brasses yielded a slope of 0.08 μg lead/cm(2)h% Pb (r(2) = 0.92). Lead release rates were used to estimate the mean daily mouthing exposure of a child to lead, according to age-specific estimates of mouthing time behavior. Calculated daily intakes were used as oral inputs for the IEUBK toxicokinetic model, predicting only marginal changes in blood lead levels (0.2 μg lead/dL or less) for children aged 0.5 to 1 years old exposed to either class of alloy. Conclusions: The results of this study as a whole support the use of migration data of metal ions, rather than total metal content, to estimate health risk from exposure to metals and metal alloys substances in children.
Keywords: Lead; Mouthing; Migration test; Alloys; Chronic exposure; Saliva
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