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Complexation- and ligand-induced metal release from 316L particles: importance of particle size and crystallographic structure
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2145-3650
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2100-8864
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2206-0082
2011 (English)In: Biometals, ISSN 0966-0844, E-ISSN 1572-8773, Vol. 24, no 6, 1099-1114 p.Article in journal (Refereed) Published
Abstract [en]

Iron, chromium, nickel, and manganese released from gas-atomized AISI 316L stainless steel powders (sized < 45 and < 4 mu m) were investigated in artificial lysosomal fluid (ALF, pH 4.5) and in solutions of its individual inorganic and organic components to determine its most aggressive component, elucidate synergistic effects, and assess release mechanisms, in dependence of surface changes using atomic absorption spectroscopy, Raman, XPS, and voltammetry. Complexation is the main reason for metal release from 316L particles immersed in ALF. Iron was mainly released, while manganese was preferentially released as a consequence of the reduction of manganese oxide on the surface. These processes resulted in highly complexing media in a partial oxidation of trivalent chromium to hexavalent chromium on the surface. The extent of metal release was partially controlled by surface properties (e.g., availability of elements on the surface and structure of the outermost surface) and partially by the complexation capacity of the different metals with the complexing agents of the different media. In general, compared to the coarse powder (< 45 mu m), the fine (< 4 mu m) powder displayed significantly higher released amounts of metals per surface area, increased with increased solution complexation capacity, while less amounts of metals were released into non-complexing solutions. Due to the ferritic structure of lower solubility for nickel of the fine powder, more nickel was released into all solutions compared with the coarser powder.

Place, publisher, year, edition, pages
2011. Vol. 24, no 6, 1099-1114 p.
Keyword [en]
Stainless steel, Powder, Complexation, Metal release, Dissolution, Inhalation
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-52543DOI: 10.1007/s10534-011-9469-7ISI: 000297117100012ScopusID: 2-s2.0-83555165202OAI: diva2:468205
Swedish Research CouncilKnut and Alice Wallenberg Foundation
QC 20111220Available from: 2011-12-20 Created: 2011-12-19 Last updated: 2012-11-26Bibliographically approved
In thesis
1. Stainless Steel in Biological Environments – Relation between Material Characteristics, Surface Chemistry and Toxicity
Open this publication in new window or tab >>Stainless Steel in Biological Environments – Relation between Material Characteristics, Surface Chemistry and Toxicity
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Triggered by the regulatory need of the industry to demonstrate safe use of their alloy products from an environmental and health perspective, and by the significant lack of metal release data and its correlation to material and surface characteristics for iron- and chromium-based alloys, a highly interdisciplinary in-depth research effort was undertaken to assess the relation between material/surface characteristics and toxicity with main emphasis on stainless steel alloys. This thesis focuses predominantly on studies made on AISI 316L both as massive sheet and as powder particles, but includes also results for other stainless steel grades and reference metals and metal oxides.


The work comprises multi-analytical bulk and surface characterizations combined with particle characterizations and corrosion investigations, all correlated with in-depth kinetic metal release (bioaccessibility) studies as a function of route of manufacture, powder particle characteristics, surface finish, stainless steel grade, solution composition, pH, acidity and complexation capacity, as well as the presence of proteins. Speciation (chemical form) measurements were in addition conducted of released chromium, and of metal species in the surface oxide. Protein interactions were investigated in terms of adsorption, protein-metal complexation both at the surface and in solution, and the relative strength of protein-stainless steel surface interaction was addressed. In vitro and in vivo toxicological studies were conducted for the same inert-gas-atomized 316L powder sized < 4µm.


Bulk and surface oxide properties, such as phase, structure, morphology, chemical and electrochemical stability, protein-surface interactions, bioavailability of released metals, were all clearly evident to largely influence the metal release process and any induced toxicity. The route of manufacture was shown to strongly influence the bulk and surface oxide characteristics of stainless steel powders, hence also their electrochemical and catalytic properties, as well as the release/dissolution of metals from the powders (Papers VIII, XIII, XIV-XVII). The release of metals from both stainless steel sheets and powders was in general low compared to pure iron or nickel metal, and highly dependent on bulk and surface characteristics, the composition, complexation capacity and buffering capacity (and pH) of the solution, as well as on many experimental factors including time and sonication (Papers VI, VIII, XI, and XVII).


Surface-protein interactions strongly enhanced the release of alloy constituents (Papers IX, XI, and XVII). Iron was preferentially released (manganese in the case of inert-gas-atomized stainless steel powders) (Papers VIII, XI, and XVII). Protein-stainless steel surface interactions were most probably governed by chemisorption at given experimental conditions (Papers XI-XII). A strong protein-adsorption was evident for all stainless steel surfaces investigated, independent of protein charge, size or structure (Paper IX). Protein-metal complexes were formed both at the surface and in solution (Papers X-XII). Differences in protein charge and type resulted in varying degrees of interaction with differences in the extent of enhanced metal release as a consequence (Papers XI-XII). The inert-gas-atomized stainless steel powder sized <4 µm induced neither any significant increase of lysis of erythrocytes (rupture of red blood cells) nor any cytotoxicity, but resulted in a slight DNA damage in in vitro toxicity measurements (Paper VI). No adverse effects were however observed in an in vivo 28-day repeated-dose inhalation study on rats using the same powder (Paper VII).


The most important bulk, surface, particle, and experimental factors governing the bioaccessibility properties of stainless steel were identified and mechanistically elucidated. Detailed knowledge of all factors is essential for accurate hazard or risk assessment of metal alloys and enables read-across possibilities with materials of the same or similar characteristics. However, in cases where data is different from known systems for one factor or more, bioaccessibility data should be generated before any risk assessment is made.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. XIV, 38 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:57
National Category
Other Chemistry Topics
urn:nbn:se:kth:diva-105521 (URN)978-91-7501-521-7 (ISBN)
Public defence
2012-12-14, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)

QC 20121126

Available from: 2012-11-26 Created: 2012-11-22 Last updated: 2012-11-26Bibliographically approved

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