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Location of cobalt impurities in stainless steel 316L and changes in composition and thickness of the surface oxide in relation to metal release in synthetic biological fluids
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science. KTH.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2100-8864
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(English)Manuscript (preprint) (Other academic) [Artistic work]
Abstract [en]

Since 2021, cobalt (Co) is in Europe classified as carcinogen in quantities exceeding 0.1 wt.-%. This affects nickel-rich stainless steels, which contain about 0.2 wt.-% Co impurities. Previous findings show the bioaccessibility of Co in stainless steel to be primarily determined by the corrosion resistance. It has been unclear whether Co is distributed heterogeneously in the alloy and the outermost surface and whether a specific location would pose a risk for Co release under specific exposure conditions. This study aimed at locating Co in austenitic stainless steel 316L (0.2 wt.-% Co) prior to and after exposure to different synthetic body fluids for 24 h at 37 °C. Time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICPMS) investigated the location of Co in the surface oxide and extent of release along with other metals (iron, chromium, nickel, and manganese) into synthetic biological fluids (gastric fluid, pH 1.5; lysosomal fluid, pH 4.5; phosphate buffered saline-PBS, pH 7.4). Co was homogeneously distributed along with metallic nickel beneath the surface oxide and co-released with other metals upon surface reformation and passivation. Exposure in PBS resulted in the incorporation of both Co and phosphate in the oxide.

Keywords [en]
stainless steel, cobalt, ToF-SIMS, XPS, passive films, bioaccessibility
National Category
Analytical Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-304811OAI: oai:DiVA.org:kth-304811DiVA, id: diva2:1611076
Note

QC 20211130

Available from: 2021-11-12 Created: 2021-11-12 Last updated: 2022-10-11Bibliographically approved
In thesis
1. Bioaccessibility, corrosion and surface properties of metals, alloys and metallic powder in biological fluids of relevance for occupational and consumer health hazard assessment
Open this publication in new window or tab >>Bioaccessibility, corrosion and surface properties of metals, alloys and metallic powder in biological fluids of relevance for occupational and consumer health hazard assessment
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

When assessing hazards of metals, alloys, and metal-containing items, the metal release (bioaccessibility) is of high importance. Triggered by increasingly stricter hazard classifications for metals, especially cobalt (Co), and limited knowledge, the aim of this doctoral thesis is to assess correlations between the metal/alloy surface characteristics, corrosion and metal release pattern in different simulated biological fluids relevant to human exposure scenarios (dermal, ingestion and inhalation, Papers I-V). In addition, occupational alloy powders (additive manufacturing, Paper III) and tattoo inks (Paper VI) were assessed in relation to potential health hazards. A reliable and reproducible in-vitro bioaccessibility test methodology was elaborated (Paper I). Generated nickel (Ni) and Co bioaccessibility data correlates with the surface and corrosion properties of the metals/alloys in the synthetic fluids, suggesting that the bioaccessible concentration, rather than bulk content, should be used for hazard assessment of Ni and Co in alloys and metals (Papers I-IV). Metallic Co was homogeneously distributed along with metallic Ni beneath the surface oxide of stainless steel 316L under different exposure conditions (Paper V). Exposure in a phosphate-containing neutral fluid resulted in the precipitation and incorporation of both Co and phosphate in the oxide (Paper V). Reused alloy powder during laser additive manufacturing processes revealed, depending on alloy type, different physicochemical properties including corrosion properties (Paper III). A large majority of the investigated tattoo inks violated existing regulations on labelling and substances of health concern (Paper VI), and Co, Ni, and other impurities were associated with iron-rich pigments. In all, this thesis presents bioaccessibility findings connected to surface characteristics relevant for hazard assessments of alloys and powders, and points towards physicochemical reasons behind the release of certain metallic impurities.

Abstract [sv]

Olika hälsorisker som till exempel hudallergi kan uppstå vid exponering för nickel och kobolt. Det är därför viktigt att förstå om olika metalliska föremål, metaller och legeringar kan frisätta dessa element i kontakt med olika kroppsvätskor. I den här doktorsavhandlingen har en metod utvecklats för att bestämma mängder av frisatt nickel och kobolt från massiva ytor och pulver av olika metalliska legeringar och rena metaller på ett jämförbart sätt och för olika exponeringsvägar (hudkontakt, inandning, förtäring). Ett annat mål har varit att undersöka om metaller som kobolt, som ofta endast befinner sig som föroreningar i legeringar, förekommer i ytoxiden eller endast i bulkmaterialet och hur det påverkar frisättningen (kobolt har nyligen omklassificierats då metallen kan orsaka cancer). Studierna har också omfattat samband mellan ytegenskaper och frisättning av metaller från metalliska pulver som används i tillverkningsindustrin och metalliska föroreningar samt undersökt hälsorisker med tatueringsfärger. Resultaten har visat att frisättningen av nickel och kobolt till olika syntetiska kroppsvätskor från metaller och legeringar ofta korrelerar väl med deras yt- och korrosionsegenskaper. Det medför att frisättnings- eller korrosionstester skulle kunna användas för att gruppera olika metaller och legeringar och bedöma deras hälsorisker, i stället för att eventuella risker baseras på legeringarnas bulksammansättningar. Legeringarnas ytoxider har ofta en skild sammansättning och en förmåga att minska frisättning av metaller på ett mycket effektivt sätt. Återanvänt pulver vid additiv tillverkning (3D-printning) kan erhålla ändrade fysikaliska och kemiska egenskaper på grund av exponeringen för laser. Innehållet av nickel, kobolt och kromföroreningar i tatueringsfärger var kopplat till andra metaller, främst järnrik röd pigment. Den här avhandlingen bidrar till att förfina riskbedömningar av metaller, legeringar, och metallinnehållande produkter.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2021. p. 48
Series
TRITA-CBH-FOU ; 2021:43
Keywords
Metal and alloy, metal release, synthetic biological fluids, surface oxide, corrosion resistance, hazard assessment
National Category
Analytical Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-304814 (URN)978-91-8040-043-5 (ISBN)
Public defence
2021-12-13, F3, Lindstedtsvägen 26, KTH and Zoom: https://kth-se.zoom.us/meeting/register/u5wodumurDIjH9UhhHbmjhRcJ6vErKrU62Kf, Stockholm, 14:00 (English)
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Note

QC 2021-11-15

Available from: 2021-11-15 Created: 2021-11-12 Last updated: 2022-06-25Bibliographically approved

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Wang, XuyingHedberg, JonasOdnevall Wallinder, Inger

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