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Degradation of zinc in saline solutions, plasma, and whole blood
KTH, School of Information and Communication Technology (ICT), Materials- and Nano Physics, Material Physics, MF. St Jude Medical Systems AB, Sweden.ORCID iD: 0000-0001-6332-0501
KTH, School of Information and Communication Technology (ICT), Materials- and Nano Physics, Material Physics, MF.
KTH, School of Information and Communication Technology (ICT), Materials- and Nano Physics, Material Physics, MF.ORCID iD: 0000-0003-1631-4293
2016 (English)In: Journal of Biomedical Materials Research. Part B - Applied biomaterials, ISSN 1552-4973, E-ISSN 1552-4981, Vol. 104, no 6, 1141-1151 p.Article in journal (Refereed) Published
Resource type
Text
Abstract [en]

The initial degradation of zinc has been investigated through exposures to simulated and real body fluids of increasing complexity: phosphate buffered saline (PBS), Ringer's saline solution, human plasma, and whole blood. Real body fluids were used to close the electrolyte gap between simulated and in vivo environment. Polarization of zinc in whole blood show a passive response not present in other electrolytes. The analysis shows a decrease in corrosion rate with time for plasma and whole blood and an increase for PBS and Ringer's. During exposure to plasma and whole blood a bi-layered corrosion product with poor adherence was formed over a uniformly corroding surface. The corrosion products comprise a mixture of inorganic material and biomolecules. Samples degrading in PBS were prone to localized corrosion and formed thick porous corrosion products of primarily zinc phosphates while in Ringer's solution a gel like layer of zinc carbonate was formed over an interface with shallow pits. The use of whole blood or plasma as electrolytes for short term in vitro evaluation of potential biodegradable metals may provide an improved understanding of the behavior in vivo, while Ringer's solution is preferred over PBS for long term degradation studies of zinc.

Place, publisher, year, edition, pages
John Wiley & Sons, 2016. Vol. 104, no 6, 1141-1151 p.
Keyword [en]
zinc, biodegradable, corrosion, blood, electrochemistry
National Category
Biomedical Laboratory Science/Technology
Identifiers
URN: urn:nbn:se:kth:diva-190549DOI: 10.1002/jbm.b.33458ISI: 000380032300010PubMedID: 26061136Scopus ID: 2-s2.0-84978640711OAI: oai:DiVA.org:kth-190549DiVA: diva2:953469
Note

QC 20160817

Available from: 2016-08-17 Created: 2016-08-12 Last updated: 2017-10-19Bibliographically approved
In thesis
1. Investigation of corrosion properties of metals for degradable implant applications
Open this publication in new window or tab >>Investigation of corrosion properties of metals for degradable implant applications
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [sv]

Nedbrytbara metaller utgör en ny klass av biomaterial med potential attersätta permanenta material i tillfälliga applikationer. Detta för att minskarisken för långvariga biverkningar. I den pågående forskningen för att utvecklanya nedbrytbara metaller är screening av nya material genom in vitro testmetoderett attraktivt alternativ för att undvika onödiga, tidskrävande ochdyrbara djurstudier.Denna avhandling fokuserar på in vitro-testning av zink- och magnesiumbaserademetaller. Inverkan av faktorer såsom sammansättningen av testlösningen,buffersystemet, belastning samt mikrostruktur hos legeringar undersöktes.Genom att använda elektrokemiska in situ tekniker såsom impedansspektroskopi(EIS) är det möjligt att studera gränssnittet mellan metall ochlösning och karakterisera egenskaperna hos den korroderande ytan. Ex situytkaraktäriseringstekniker som svepelektronmikroskopi och infraröd spektroskopianvändes sedan för att komplettera resultaten av de elektrokemiskamätningarna.Korrosionen av zink i Ringer’s lösning fanns vara närmare in vivo korrosionän korrosionen i fosfatbuffrad saltlösning (PBS). Ringers lösning är därför denföredragna testmiljön för långsiktig utvärdering av zinkbaserade metallerDet biologiska buffersystemet (CO2/H2CO3) bör företrädesvis användasför att stabilisera pH-värdet på testlösningen vid magnesiumnedbrytning. NärHEPES användes för att stabilisera pH ökade korrosionshastigheten på grundav bildning av mindre skyddande skikt av korrosionsproduktMöjligheten att använda helblod och plasma som mer kliniskt relevantatestmiljöer utvärderades och befanns producera reproducerbara resultat.Bildning av ett korrosionsskikt bestående av både organiskt och oorganisktmaterial detekterades på zink i både plasma och helblod.När zink prover i helbod utsattes för belastning förhindrade korrosionsskiktetbildningen av mikrosprickor och förtidigt brott av provet. Det varvidare möjligt att detektera tidig sprickbildning på grund av belastning avMagnesium AZ61-legering med EIS.Adsorption av organiska species på zinkytan under anodisk polariseringökar yttäckningen av Zn-joner i helblod. Den ökade yttäckningen leder sedantill utfällningen av ett skyddande skikt av zinkfosfater och en minskadkorrosionshastighet vid högre potentialer.Korrosion av Zn-Mg och Zn-Ag legeringar i Ringers lösning befanns skevia selektiv upplösning. Lokal utfällning av korrosionsprodukter och bildningav ett poröst, mindre skyddande skikt av korrosionsprodukter hittades påZn-Mg legeringar. Den selektiva upplösningen av Zn-Ag legering orsakade enanrikning av AgZn3 vilket kan påverka biokompatibiliteten av ett implantatmed tiden.

Abstract [en]

Degradable metallic implants are a new class of biomaterials with potentialto replace permanent materials in temporary applications to reduce therisk of long term adverse effects.This thesis focuses on in vitro testing of zinc and magnesium based metals.As new degradable metals are developed screening of new materials within vitro test methods is an attractive option to avoid unnecessary, time consumingand expensive animal studies. The influence of factors such as ioniccomposition of the test solution, buffer system, strain and alloy compositionwas investigated. By employing electrochemical in situ techniques such asimpedance spectroscopy it is possible to study the metal-solution interfaceand determine the properties of the corroding surface. Ex situ surface characterizationtechniques such as scanning electron microscopy and infraredspectroscopy were then used to complement the results of the electrochemicalmeasurements.The importance of appropriate selection of the test solution is highlightedin this work. Zinc was found to corrode in Ringer’s solution by a mechanismcloser to in vivo corrosion than in a phosphate buffered saline solution(PBS).Ringer’s solution is therefore the more appropriate test environment for longterm evaluation of zinc based metals.When evaluating the corrosion of Zn-Mg and Zn-Ag alloys in Ringer’ssolution selective dissolution was found to occur for both types of alloys. Localprecipitation and formation of a porous, less protective, layer of corrosionproducts was found for Zn-Mg alloys. The selective dissolution of Zn-Agalloy caused an enrichment of AgZn3 on the surface which may affect thebiocompatibility of the alloy.The use of HEPES to maintain the pH of the test solution increasedthe corrosion rate of magnesium due to formation of a less protective layerof corrosion products. Magnesium corrosion should therefore preferably bestudied in solutions where the pH is maintained by the biological buffer systemCO2/H2CO3.In addition to saline solutions human whole blood and plasma were evaluatedas more clinically relevant in vitro environments. They were found toproduce reproducible results and to be suitable for short term experiments.Formation of a corrosion product layer comprised of both organic and inorganicmaterial was detected on zinc in both plasma and whole blood.During anodic polarization the adsorption of organic species on the zincsurface was found to increase the surface coverage of Zn ions in whole blood.The increased surface coverage then allowed for precipitation of a protectivelayer of Zn5(PO4)3 and a subsequent decrease in corrosion rate at higherpotentials.When subjecting zinc samples to strain the organic/inorganic corrosionproduct formed in whole blood was observed by impedance spectroscopy toprevent micro cracking and premature failure.The cracking of magnesium alloy samples under applied strain was alsocharacterized by impedance. Changes in surface properties due to crack initiation

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2017. 80 p.
Series
TRITA-FYS, ISSN 0280-316X ; 2017:58
Keyword
biodegradable, metal, zinc, magnesium, corrosion, electrochemistry
National Category
Bio Materials Metallurgy and Metallic Materials
Research subject
Materials Science and Engineering
Identifiers
urn:nbn:se:kth:diva-215970 (URN)978-91-7729-528-0 (ISBN)
Public defence
2017-11-10, sal C (Sven-Olof Öhrvik), Electrum, kistagången 16, kista, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council
Note

QC 20171019

Available from: 2017-10-19 Created: 2017-10-19 Last updated: 2017-10-19Bibliographically approved

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