| 1. |
- Atapour, Masoud, et al.
(författare)
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Metal release from stainless steel 316L in whey protein - And simulated milk solutions under static and stirring conditions
- 2019
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Ingår i: Food Control. - : ELSEVIER SCI LTD. - 0956-7135 .- 1873-7129. ; 101, s. 163-172
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Tidskriftsartikel (refereegranskat)abstract
- Stainless steel is an important transport and processing contact material for bovine milk and dairy products. Release (migration) of metals, ions, complexes or wear debris/particles, and metal-induced protein aggregation in such environments are hence important to consider both from a corrosion and food safety perspective. This study aims on investigating the release of iron (Fe), chromium (Cr), and nickel (Ni) from AISI 316L stainless steel in contact with whey protein solutions relevant for protein drinks, and on how the whey proteins are influenced by stirring with a magnetic stir bar and metal release. Mechanistic insight is gained by parallel investigations of metal release from two reference non-protein containing solutions, a metal-complexing (citrate-containing) simulated milk solution (SMS) and a low complexing phosphate buffered saline solution (PBS). All immersion exposures were conducted at pH 6.8 for 0.5, 4, 24 and 48 hat room temperature at static and stirring conditions. All solutions and samples were investigated using different chemical, spectroscopic, microscopic, and electrochemical methods. Significantly higher amounts of Fe, Cr, and Ni were released into the whey protein solution (80 g/L) as compared to SMS and PBS. Strong enrichment of Cr in the surface oxide and reduction of the surface oxide thickness were associated with a higher amount of Ni release in the metal-complexing solutions (SMS and whey protein) compared with PBS. Stirring conditions resulted in higher amounts of metal release, enrichment of Cr in the surface oxide, and clear signs of wear of the 316L surface in all solutions compared to static conditions. The wear mechanism in the whey protein solution was different as compared to corresponding processes in SMS and PBS, involving an etching-like process and larger-sized wear debris. Electrochemical measurements at static conditions confirmed observed differences between the solutions, with the lowest corrosion resistance observed for coupons exposed in the whey protein solution, followed by SMS and PBS. Released metals in solution from the 316L coupons in contact with the whey protein solution resulted in enhanced rates of protein aggregation and precipitation of protein aggregates from solution. Further studies should be made to investigate other relevant test conditions and assess toxicological risks.
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| 2. |
- Besharat, Zahra, et al.
(författare)
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Mixed monolayers of alkane thiols with polar terminal group on gold : Investigation of structure dependent surface properties
- 2016
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Ingår i: Journal of Colloid and Interface Science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 484, s. 279-290
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Tidskriftsartikel (refereegranskat)abstract
- Adsorption of thiols with cationic or anionic terminal group on gold has been studied from mixed solutions of 11-Amino-1-undecanethiol (AUT) and 3-Mercaptopropionic acid (MPA) using Quartz Crystal Microbalance with Dissipation (QCM-D), X-ray Photoelectron Spectroscopy (XPS), atomic force microscopy (AFM) and contact angles. The goal is to probe the nature of such layers, and the additivity or otherwise of the pH responsiveness, with a view to evaluate their suitability as smart materials. For each of the two pure (unmixed) cases, ordered molecular monolayers are formed with sulfur binding to gold and the alkane chain pointing out from the surface as expected. Adsorption from the thiol mixtures, however, leads to a more complex behaviour. The surface concentration of thiols from the mixtures, as determined by QCM-D, is considerably lower than for the pure cases and it reaches a minimum at a 3:1 MPA/AUT relative concentration in the solution. The XPS results confirm a reduction in adsorbed amount in mixtures with the lowest overall intensity for the 3:1 ratio. Monolayers formed from mixtures display a wettability which is much lower and less pH sensitive. Collectively these results confirm that for adsorption from mixed systems, the configuration is completely different. Complex formation in the mixed solutions leads to the adsorption of molecules parallel to the surface in an axially in-plane configuration. This parallel layer of thiols is mechanically relatively robust to nano-shaving based on AFM measurements. These results will have a significant impact on the design of biomimetic surface coatings particularly when mixtures of oppositely charged molecules are present on the surface, as is commonly the case in biological, proteinaceous surfaces (e.g. hair and skin).
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| 3. |
- Cappellini, Francesca, et al.
(författare)
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Mechanistic insight into reactivity and (geno)toxicity of well-characterized nanoparticles of cobalt metal and oxides
- 2018
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Ingår i: Nanotoxicology. - : Taylor & Francis. - 1743-5390 .- 1743-5404. ; 12:6, s. 602-620
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Tidskriftsartikel (refereegranskat)abstract
- An increasing use of cobalt (Co)-based nanoparticles (NPs) in different applications and exposures at occupational settings triggers the need for toxicity assessment. Improved understanding regarding the physiochemical characteristics of Co metal NPs and different oxides in combination with assessment of toxicity and mechanisms may facilitate decisions for grouping during risk assessment. The aim of this study was to gain mechanistic insights in the correlation between NP reactivity and toxicity of three different Co-based NPs (Co, CoO, and Co3O4) by using various tools for characterization, traditional toxicity assays, as well as six reporter cell lines (ToxTracker) for rapid detection of signaling pathways of relevance for carcinogenicity. The results showed cellular uptake of all NPs in lung cells and induction of DNA strand breaks and oxidative damage (comet assay) by Co and CoO NPs. In-depth studies on the ROS generation showed high reactivity of Co, lower for CoO, and no reactivity of Co3O4 NPs. The reactivity depended on the corrosion and transformation/dissolution properties of the particles and the media highlighting the role of the surface oxide and metal speciation as also confirmed by in silico modeling. By using ToxTracker, Co NPs were shown to be highly cytotoxic and induced reporters related to oxidative stress (Nrf2 signaling) and DNA strand breaks. Similar effects were observed for CoO NPs but at higher concentrations, whereas the Co3O4 NPs were inactive at all concentrations tested. In conclusion, our study suggests that Co and CoO NPs, but not Co3O4, may be grouped together for risk assessment.
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| 4. |
- Chang, Tingru, et al.
(författare)
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Analysis of historic copper patinas. Influence of inclusions on patina uniformity
- 2017
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Ingår i: Materials. - : MDPI AG. - 1996-1944. ; 10:3
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Tidskriftsartikel (refereegranskat)abstract
- The morphology and elemental composition of cross sections of eight historic copper materials have been explored. The materials were taken from copper roofs installed in different middle and northern European environments from the 16th to the 19th century. All copper substrates contain inclusions of varying size, number and composition, reflecting different copper ores and production methods. The largest inclusions have a size of up to 40 μm, with most inclusions in the size ranging between 2 and 10 μm. The most common element in the inclusions is O, followed by Pb, Sb and As. Minor elements include Ni, Sn and Fe. All historic patinas exhibit quite fragmentized bilayer structures, with a thin inner layer of cuprite (Cu2O) and a thicker outer one consisting mainly of brochantite (Cu4SO4(OH)6). The extent of patina fragmentation seems to depend on the size of the inclusions, rather than on their number and elemental composition. The larger inclusions are electrochemically nobler than the surrounding copper matrix. This creates micro-galvanic effects resulting both in a profound influence on the homogeneity and morphology of historic copper patinas and in a significantly increased ratio of the thicknesses of the brochantite and cuprite layers. The results suggest that copper patinas formed during different centuries exhibit variations in uniformity and corrosion protection ability.
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| 5. |
- Chang, Tingru
(författare)
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Atmospheric corrosion of copper and copper-based alloys in architecture : from native surface oxides to fully developed patinas
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Copper and copper-based alloys are commonly used in both ancient and modern architecture. This requires an in-depth fundamental and applied understanding on their atmospheric corrosion behavior at different climatic, environmental and pollutant levels and how these parameters influence e.g. corrosion initiation, patina characteristics, aesthetic appearances, corrosion rates, and runoff rates. This doctoral thesis elucidates the role of native surface oxides on the corrosion performance, corrosion initiation, formation and evolution of corrosion products from hours to months, years and even centuries, to diffuse dispersion of metals from Cu metal/Cu alloy surfaces focusing on the roles of alloying elements, microstructure, and deposition of chlorides. In-depth investigations have been performed at both laboratory and field conditions on commercial Cu metal and copper-based alloys of a golden alloy (Cu5Zn5Al1Sn) and Sn-bronzes (Cu4Sn, Cu6Sn). Patina characteristics and relations to the presence of microstructural inclusions have in addition been investigated for historic patinas of Cu metal roofing of different age and origin, highlighted with data for a 400 years old Cu patina exposed at urban conditions.A multi-analytical approach comprising microscopic, spectroscopic and electrochemical methods was employed for in-depth investigations of surface characteristics and bulk properties. Electron backscattered diffraction (EBSD) was utilized to characterize the microstructure. Auger electron spectroscopy (scanning-AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES) were employed for surface chemical compositional analysis, and atomic absorption spectroscopy (AAS) to assess the amount of metal release from the patinas. Cathodic reduction (CR) and electrochemical impedance spectroscopy (EIS) were used to assess the amount and corrosion resistance of corrosion products formed at laboratory conditions. Confocal Raman micro-spectroscopy (CRM), infrared reflection absorption spectroscopy (IRAS) and grazing incidence X-ray diffraction (GIXRD) were used to identify the phases of corrosion products. Colorimetry was used to assess surface appearances.Cu5Zn5Al1Sn and Cu4Sn/Cu6Sn exhibit favorable bulk properties with respect to corrosion in terms of smaller grain size compared with Cu metal and show non-significant surface compositional variations. The presence of multi-component native oxides predominantly composed of Cu2O enriched with Sn-oxides on Cu4Sn/Cu6Sn, and with ZnO, SnO2 and Al2O3 on Cu5Zn5Al1Sn, improves the barrier properties of the native surface oxides and the overall corrosion resistance of Cu4Sn/Cu6Sn and Cu5Zn5Al1Sn. The formation of Zn/Al/Sn-containing corrosion products (e.g. Zn5(CO3)2(OH)6 and Zn6Al2(OH)16CO3·4H2O) significantly reduces the corrosion rate of Cu5Zn5Al1Sn in chloride-rich environments. Alloying with Sn reduces the corrosion rate of Sn-bronze at urban environments of low chloride levels but results in enhanced corrosion rates at chloride-rich marine conditions.A clear dual-layer structure patina was observed for centuries-old naturally patinated copper metal with an origin from the roof of Queen Anne's Summer Palace in Prague, the Czech Republic. The patina comprises an inner sub-layer of Cu2O and an outer sub-layer of Cu4SO4(OH)6/Cu3SO4(OH)4. Abundant relatively noble inclusions (mainly rosiaite (PbSb2O6)) were observed and incorporated in both the copper matrix and the patina. The largest inclusions of higher nobility than the surrounding material create significant micro-galvanic effects that result in a fragmentized patina and large thickness ratios between the Cu4SO4(OH)6/Cu3SO4(OH)4 and the Cu2O sub-layer, investigated via a statistical analysis of inclusions and patina characteristics of eight different historic urban copper patinas.
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| 6. |
- Chang, Tingru, et al.
(författare)
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Synergistic effects of gelatin and convection on copper foil electrodeposition
- 2016
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Ingår i: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 211, s. 245-254
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Tidskriftsartikel (refereegranskat)abstract
- Copper foil electrodeposition has been explored using a pure titanium rotating disk electrode (RDE) in acidic electrolytes containing gelatin and/or chloride ions under different convection conditions. In the plating bath without gelatin, the results indicate that stronger convection promotes hydrogen evolution, which reduces the current efficiency during copper plating. Gelatin restrains the growth of copper grains in the lateral direction parallel to the surface. This results in grain refinement on the shiny side, an increase in local grain misorientation and in internal stresses on both the shiny and the matte side, and a reduction in their internal stress difference. At strong convection conditions and with gelatin present, copper deposits as strip-like grains along the centrifugal direction of the cross section, and finally forms a spiral-shaped pattern on the matte side. The causes of these features are discussed in detail. The combined influences of hydrogen and gelatin adsorption are further elaborated in a model for a copper deposition. The current investigation suggests that a moderate convection (somewhat lower than 1000 rpm) and a concentration of 2 ppm gelatin in the plating bath are sufficient for copper foil fabrication in the presence of chloride ions (20 ppm).
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| 7. |
- Chang, Tingru, et al.
(författare)
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The golden alloy Cu-5Zn-5Al-1Sn : A multi-analytical surface characterization
- 2018
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Ingår i: Corrosion Science. - : Elsevier. - 0010-938X .- 1879-0496. ; 131, s. 94-103
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Tidskriftsartikel (refereegranskat)abstract
- The golden alloy Cu-5Zn-5Al-1Sn has found many applications because of its appearance and resistance to tarnishing. The microstructure and multi-component surface oxide of Cu-5Zn-5Al-1Sn have been investigated through a multi-analytical approach. Compared to commercial Cu metal, Cu-5Zn-5Al-1Sn has significantly smaller grains and higher fraction of coherent twin boundaries. The 5-10 nm thick oxide formed after diamond polishing has four identified sub-oxides all contributing to the overall corrosion resistance. Cu2O is mainly located in the outer part, followed by ZnO, SnO2 and Al2O3 closer to the alloy substrate. The latter three possess barrier properties, while Cu2O exhibits a more complex structure.
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| 8. |
- Chang, Tingru, et al.
(författare)
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The golden alloy Cu5Zn5Al1Sn : Patina evolution in chloride-containing atmospheres
- 2018
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Ingår i: Corrosion Science. - : Elsevier. - 0010-938X .- 1879-0496. ; 133, s. 190-203
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Tidskriftsartikel (refereegranskat)abstract
- The influence of chloride deposition on the formation, evolution and barrier properties of the patina formed on CuSZn5Al1Sn used for architectural cladding is explored via long-term marine field exposures and laboratory investigations. The presence of Cu2O, ZnO, Al2O3 and SnO2 within the inner part of the patina and intercalation of SnO2, Zn-5(CO3)(2)(OH)(6), Zn6Al2(OH)(16)CO3 center dot 4H(2)O, Zn-5(OH)(8)Cl-2 center dot H2O within its outer part, predominantly composed of Cu-2(OH)(3)Cl, significantly reduce the chloride-induced corrosion compared with Cu metal. The intercalation of zinc-rich corrosion products within the patina and not at the top-surface explain their marginal influence on the runoff process that mainly occurs at the outmost surface.
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| 9. |
- Chang, Tingru, et al.
(författare)
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The role of Sn on the long-term atmospheric corrosion of binary Cu-Sn bronze alloys in architecture
- 2019
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Ingår i: Corrosion Science. - : Elsevier Ltd. - 0010-938X .- 1879-0496. ; 149, s. 54-67
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Tidskriftsartikel (refereegranskat)abstract
- The role of Sn on the atmospheric corrosion performance of binary Cu-Sn bronze alloys (4–6 wt.% Sn) compared with Cu metal used in outdoor architecture is elucidated in terms of microstructure, native surface oxide composition, patina evolution, corrosion rates, appearance and metal release. Results are presented for non-exposed surfaces and surfaces exposed at different urban and marine sites in Europe up to 5 years and based on multi-analytical findings from microscopic, spectroscopic, electrochemical and chemical investigations. Alloying influenced the corrosion, aesthetic appearance and patina evolution, differently for urban and marine sites, whereas no effects were observed on the release pattern. © 2019 The Authors
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| 10. |
- Chang, Tingru, et al.
(författare)
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Understanding the Barrier Layer Formed via Adding BTAH in Copper Film Electrodeposition
- 2019
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Ingår i: Journal of the Electrochemical Society. - : ELECTROCHEMICAL SOC INC. - 0013-4651 .- 1945-7111. ; 166:2, s. D10-D20
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Tidskriftsartikel (refereegranskat)abstract
- The influence of surface adsorption of benzotriazole (BTAH) and of chloride ions (Cl-) on the kinetics of copper electrodeposition/dissolution in copper sulfate solutions and on copper deposit characteristics have been investigated using electrochemical quartz crystal microbalance (EQCM) combined with cyclic voltammetry (CV). The addition of BTAH alone increases the overpotential of copper deposition, whereas a Cu(I)BTA complex forms at potentials higher than 0.08 V (vs. SCE) accompanied with the occurrence of copper anodic dissolution. With simultaneous addition of BTAH and Cl-, surface adsorption of Cl- competes with that of BTAH during the initial stage of copper nucleation. Different cuprous reaction intermediates form in the examined potential range -0.4 to 0.3 V (vs. SCE), which partly eliminate the favorable effect of BTAH on the deposited copper. A BTAH-containing adsorbed layer formed on the matte side of electrodeposited copper film in the presence of BTAH with or without Cl-, exhibiting a barrier surface property and an improved corrosion resistance compared with the copper film electrodeposited in the electrolyte without addition of BTAH.
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