Numerical Modelling of Effects of Biphasic Layers of Corrosion Products to the Degradation of Magnesium Metal In Vitro

Magnesium (Mg) is becoming increasingly popular for orthopaedic implant materials. Its mechanical properties are closer to bone than other implant materials, allowing for more natural healing under stresses experienced during recovery. Being biodegradable, it also eliminates the requirement of further surgery to remove the hardware. However, Mg rapidly corrodes in clinically relevant aqueous environments, compromising its use. This problem can be addressed by alloying the Mg, but challenges remain at optimising the properties of the material for clinical use. In this paper, we present a mathematical model to provide a systematic means of quantitatively predicting Mg corrosion in aqueous environments, providing a means of informing standardisation of in vitro investigation of Mg alloy corrosion to determine implant design parameters. The model describes corrosion through reactions with water, to produce magnesium hydroxide Mg(OH)2, and subsequently with carbon dioxide to form magnesium carbonate MgCO3. The corrosion products produce distinct protective layers around the magnesium block that are modelled as porous media. The resulting model of advection–diffusion equations with multiple moving boundaries was solved numerically using asymptotic expansions to deal with singular cases. The model has few free parameters, and it is shown that these can be tuned to predict a full range of corrosion rates, reflecting differences between pure magnesium or magnesium alloys. Data from practicable in vitro experiments can be used to calibrate the model’s free parameters, from which model simulations using in vivo relevant geometries provide a cheap first step in optimising Mg-based implant materials.

[1]  A. Concha Theory of Mixtures , 2014 .

[2]  Ke Yang,et al.  In vivo evaluation of biodegradable magnesium alloy bone implant in the first 6 months implantation. , 2009, Journal of biomedical materials research. Part A.

[3]  Roberto Natalini,et al.  A Mathematical model of copper corrosion , 2012, 1211.6938.

[4]  M. Schlesinger,et al.  Corrosion of magnesium and its alloys , 2009 .

[5]  Anneke Loos,et al.  Magnesium alloys: A stony pathway from intensive research to clinical reality. Different test methods and approval-related considerations. , 2017, Journal of biomedical materials research. Part A.

[6]  Antonio Fasano,et al.  Mathematics and Monument Conservation: Free Boundary Models of Marble Sulfation , 2008, SIAM J. Appl. Math..

[7]  Alexis M Pietak,et al.  Magnesium and its alloys as orthopedic biomaterials: a review. , 2006, Biomaterials.

[8]  N E Saris,et al.  Magnesium. An update on physiological, clinical and analytical aspects. , 2000, Clinica chimica acta; international journal of clinical chemistry.

[9]  S. S. Pathak,et al.  Magnesium-Based Sacrificial Anode Cathodic Protection Coatings (Mg-Rich Primers) for Aluminum Alloys , 2012 .

[10]  Y. Zaika,et al.  Modelling of zirconium alloy hydrogenation , 2016 .

[11]  Akiko Yamamoto,et al.  Effect of inorganic salts, amino acids and proteins on the degradation of pure magnesium in vitro , 2009 .

[12]  Frank Witte,et al.  Progress and Challenge for Magnesium Alloys as Biomaterials , 2008 .

[13]  Prashant N. Kumta,et al.  In vivo study of magnesium plate and screw degradation and bone fracture healing. , 2015, Acta biomaterialia.

[14]  A. Campo,et al.  Adaptation of the Method Of Lines ( MOL ) to the MATLAB Code for the Analysis of the Stefan Problem , 2014 .

[15]  J. Rumble CRC Handbook of Chemistry and Physics , 2019 .

[16]  A. Wennerberg,et al.  Influence of Magnesium Alloy Degradation on Undifferentiated Human Cells , 2015, PloS one.

[17]  F. Feyerabend,et al.  A simple model for long‐time degradation of magnesium under physiological conditions , 2018 .

[18]  R. Larson A Physical and Mathematical Model for the Atmospheric Sulfidation of Copper by Hydrogen Sulfide , 2002 .

[19]  Guang-Ling Song,et al.  Control of biodegradation of biocompatable magnesium alloys , 2007 .

[20]  M. Escudero,et al.  Modeling in vivo corrosion of AZ31 as temporary biodegradable implants. Experimental validation in rats. , 2014, Materials science & engineering. C, Materials for biological applications.

[21]  Yufeng Zheng,et al.  Accelerating Corrosion of Pure Magnesium Co-implanted with Titanium in Vivo , 2017, Scientific Reports.

[22]  Edward L Cussler,et al.  Diffusion: Mass Transfer in Fluid Systems , 1984 .

[23]  L. Geris,et al.  Mathematical modelling of the degradation behaviour of biodegradable metals , 2016, Biomechanics and Modeling in Mechanobiology.

[24]  Jörg F. Löffler,et al.  Assessing the degradation performance of ultrahigh-purity magnesium in vitro and in vivo , 2015 .

[25]  Robert E. Melchers,et al.  Mathematical modelling of the diffusion controlled phase in marine immersion corrosion of mild steel , 2003 .

[26]  Donghui Zhu,et al.  Collagen Self-Assembly on Orthopedic Magnesium Biomaterials Surface and Subsequent Bone Cell Attachment , 2014, PloS one.

[27]  Tingting Wu,et al.  An arbitrary Lagrangian–Eulerian model for studying the influences of corrosion product deposition on bimetallic corrosion , 2013, Journal of Solid State Electrochemistry.

[28]  R. Goodall,et al.  Processing of Magnesium Porous Structures by Infiltration Casting for Biomedical Applications , 2014 .

[29]  G. Song,et al.  Understanding Magnesium Corrosion—A Framework for Improved Alloy Performance , 2003 .

[30]  Frank Witte,et al.  Degradable biomaterials based on magnesium corrosion , 2008 .

[31]  M. Ehrensberger,et al.  Corrosion and mechanical performance of AZ91 exposed to simulated inflammatory conditions. , 2016, Materials science & engineering. C, Materials for biological applications.

[32]  Yufeng Zheng,et al.  Corrosion of magnesium and magnesium-calcium alloy in biologically-simulated environment , 2014 .

[33]  E. Kim Functional Neuroradiology: Principles and Clinical Applications , 2014, The Journal of Nuclear Medicine.

[34]  N Birbilis,et al.  Assessing the corrosion of biodegradable magnesium implants: a critical review of current methodologies and their limitations. , 2012, Acta biomaterialia.

[35]  Michael Böhm,et al.  A moving-boundary problem for concrete carbonation:global existence and uniqueness of weak solutions , 2009 .

[36]  A. A. Bakir,et al.  Porous Biodegradable Metals for Hard Tissue Scaffolds: A Review , 2012, International journal of biomaterials.

[37]  D. Thierry,et al.  Corrosion product formation during NaCl induced atmospheric corrosion of magnesium alloy AZ91D , 2007 .

[38]  C. Chainais-Hillairet,et al.  On the existence of solutions for a drift-diffusion system arising in corrosion modelling , 2012, 1212.3279.

[39]  C. Grillo,et al.  Time-Lapse Evaluation of Interactions Between Biodegradable Mg Particles and Cells , 2016, Microscopy and Microanalysis.

[40]  C. You,et al.  Effects of grain size on the corrosion resistance of pure magnesium by cooling rate-controlled solidification , 2015, Frontiers of Materials Science.

[41]  A. McGoron,et al.  Biodegradable Magnesium Alloys: A Review of Material Development and Applications , 2012, Journal of biomimetics, biomaterials, and tissue engineering.