Corrosion Mechanisms of Diamond-like Carbon Coated Interlayers & Interfaces

Emilija Ilic
EPFL, 2019
EPFL thesis

Abstract

Diamond-like carbon (DLC) coatings can improve the wear resistance of articulating implants. However despite successful in-vitro testing, some DLC coated joint replacements had to be revised prematurely, mainly due to coating delamination induced by corrosion at the substrate/DLC interface. Body fluid will enter defective coating sites and if the reactively formed interface or interlayer materials are instable in the confined fluid, they with dissolve, resulting in delamination of the DLC and ultimate failure of the implant. The aim of this thesis is therefore to investigate the corrosion mechanisms responsible for delamination at a substrate/DLC interface in body-like media. This is achieved by developing and implementing experimental methodologies addressing/simulating aggravating factors such as confinements/crevices, galvanic coupling, stress and fatigue on the interface to investigate corrosion initiation, propagation, and failure.

Firstly, corrosion initiation and galvanic coupling risk are addressed with a methodology for accessing and characterizing the reactivity of buried interlayers. The interlayer is revealed by ion beam polishing, forming a wedge-like profile of the substrate/interlayer/DLC. The composition and chemical state of the interlayer/interface is determined by Auger electron spectroscopy. Reactive interlayers/interfaces, Si, titanium (Ti) and chromium (Cr), formed new phases (carbides and oxides). These new materials are then characterized with a local-electrochemical microcapillary technique. Cr and Si-DLC based interlayers presented good passive behavior, while a Si interlayer corroded in bovine-based wear test fluid (HyClone® WTF). The influence of coating defects on the current response of DLC surfaces was also investigated by varying the exposed working area (cm2 to µm2 range).

To address the failure case of a TiAlV/Si/DLC implant, the influence of confinements/crevices on corrosion propagation is investigated. It is shown that Si is highly vulnerable to corrosion in confined conditions. Pitting corrosion susceptibility is found in a crevice, whereas a Si dissolution rate of ca. 3.6 nm/h at 37 °C occurs within a confined area. The corrosion rates increased at elevated temperatures and yielded linear Arrhenius relations, with activation energies of 106 KJ/mol in phosphate buffered saline (PBS) and 109 KJ/mol in HyClone® WTF. Phosphorous species enhanced Si dissolution, while chlorides were not so influential. Galvanic coupling with Ti and applied stress further accelerated the Si dissolution.

Finally, corrosion related fracture of a CoCrMo/DLC interface is investigated by applying static and cyclic load. A reciprocating sliding rig is utilized to determine the number of sliding cycles required for interface delamination to occur at a critical load, in PBS at 37 °C. The results followed a Wöhler curve relation. Small O2 contaminations (0.5 and 1.0%) at the interface adversely affected the CF behaviour by lowering the critical load and endurance limit. The fitted Wöhler curves could be extrapolated and were found to be in good agreement with long-term experimental results previously obtained on an implant in a spinal disk simulator.

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Emilija Ilic
EPFL, 2019
EPFL thesis

Abstract

Official source

https://infoscience.epfl.ch/record/270631?ln=en

About this result

Related concepts (20)

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Related publications

A methodology for characterizing the electrochemical stability of DLC coated interlayers and interfaces

Roland Hauert, Emilija Ilic, Stefano Mischler, Patrik Schmutz

DLC coatings are often deposited on Si and Cr based adhesion-promoting interlayers to mitigate stress at the DLC/substrate interface. Interlayers reduce the likelihood of mechanical coating delamination. However, their chemical stability at miniature DLC coating defects, such as pores and micro-pinholes, may be adversely affected in a corrosive environment, such as the human body where DLC coated implants are envisaged. An experimental methodology is presented for accessing and characterizing the electrochemical reactivity of buried interlayers and interfaces. The interlayer, with its interfaces, is revealed by ion beam polishing at an angle, forming a wedge-like profile of the substrate/interlayer/DLC system. The chemical binding and composition of the interlayer/interface is determined by Auger electron spectroscopy (AES), and the susceptibility of the different interfaces to carbide formation and oxidation is identified. It is shown that pure interlayer/interface materials can be obtained for the model Co interlayer. On the other hand, for more reactive materials such as Si, Ti and Cr, the formation of new interface phases was observed. These different new materials are characterized for their corrosion susceptibility with a local-electrochemical microcapillary technique both at open circuit potential (OCP) and under potentiodynamic polarization. Cr and Si-DLC based interlayers presented good passive behavior, while a Si interlayer corroded in bovine-based wear test fluid (HyClone (R) WTF). An analogous degradation is found after a long-term immersion experiment and failed implant cases. The influence of coating defects distribution on the current response of DLC surfaces during electrochemical measurements was also investigated by varying the exposed area (from the cm(2) to the mu m(2) range). Microscale characterization allowed for a better representation of the intrinsic reactivity of DLC, while larger areas were highly dependent on the underlying interlayer.

ELSEVIER SCIENCE SA2019

Modèle d'évolution de l'état des ponts-routes en béton

Guido Roelfstra

The management of existing road infrastructures is a multidisciplinary activity that involves structural engineering, material science, management, economics and ecology. The objective is to achieve maximum availability of road links at minimum societal costs. Recently, tools (Bridge Management Systems, BMSs) have been developed to help decision makers to determine the optimal management strategies within available resources. The condition development model is a key element of the BMSs. Currently this model is using empirical approach making use of data collected during inspections and is formulated with Markov chains. The assessment units are structural elements and these are classified into condition classes according to their visual appearance. The condition assessment is therefore rather subjective since no measurements are involved in it. Consequently, the condition development based on visual inspections will reflect this subjectivity. In order to improve the objectivity of condition forecasts physical and chemical phenomena governing deterioration has to be incorporated in the condition development model. Observations made on a bridge sample representative of the Swiss highway bridges showed that chloride-induced corrosion is the main deterioration mechanism. For this reason this research was focused upon modeling the chloride-induced corrosion. In this research, the condition development model is established, based physical and chemical phenomena involved in chloride induced corrosion. This analytical model is able to yield quantitative results on condition development. Accuracy and availability of input data govern the level of accuracy of such an analytical model. The existing knowledge on chloride induced corrosion and inspection techniques available on site are examined in order to develop a simple and reliable condition development model. Firstly, non-destructive testing methods are used in addition to visual observations, to determine quantitative values (permeability and thickness of the concrete cover) of parameters governing the segment deterioration. The structural elements are divided into areas i.e. segments where the parameters governing chloride-induced corrosion are assumed to be constant. It is proposed to divide structural elements into segments based on three concrete cover permeability classes, concrete cover thickness and three types of surface exposures to chloride contaminated water. Secondly, a chloride transport model is developed to simulate the real exposure of reinforcement to chloride contaminated water, taking into consideration the transport mechanisms of water and chloride ions. Simulations are performed for the various segment parameters that have been identified in the segmental approach. Thirdly, a relation is established between the free chloride ion content and the corrosion initiation probability. Using the results of the chloride transport model, the development of the corrosion initiation is determined for road bridges segments. An analysis is made to predict the corrosion initiation time of existing bridges as a function of their segment parameters (exposure and concrete cover permeability and thickness), but also to establish recommendations for the construction of new bridges. Fourthly, the corrosion rate i.e. loss of steel cross-section is then determined according to the concrete cover permeability and the exposure to chloride contaminated water. Fifthly, the results of the presented mode1 are mapped to conditions States as defined in the BMSs. Three degradation matrices (Markov chains) are determined, corresponding to three condition developments: favorable, normal and unfavorable. The three condition developments can be estimated for given quantitative values of the concrete cover permeability, thickness and surface exposure to chloride-contaminated water. In this way, the segment parameters may be used in BMSs to forecasts future condition of segments, elements and the whole structure. Finally the structural behaviour of the concrete road-bridges until failure is studied. The determinant failure scenarios are identified for each bridge type and a case study is performed on the sample representative for the Swiss highway bridges. For this purpose the determinant segments for the structural safety are identified. Additionally the required concrete cover depth for a service life of 50 and 100 years is expressed as a function of the permeability and the exposure to chloride contaminated water. This research outlines the need to measure the concrete cover permeability and thickness with non-destructive test methods as well as to determine the exposure to chloride contaminated water. These values are essential to predict the condition development of concrete road bridges.

EPFL2001

The main objectives of this work are 2-fold : The development of a novel type of composite material based on carbon nanofibers supported on sintered metal fibers filters (CNF/SMF) and to explore the use of this material as a catalytic support for a model reaction: selective hydrogenation of acetylene. The advantages of this novel support are: Due to carbon nanofibers, it combines a graphitic structure with a high specific surface area without microporosity. Supported carbon nanofibers can be used in a fixed bed reactor without very high pressure drop. Combination of two materials with high thermal conductivity gives a composite which keeps this property. It is suitable for highly exo/endothermic reactions, diminishing temperature gradients in the catalytic bed. The synthesis of carbon nanofibers on SMF filters was carried out by ethane catalytic decomposition at 655°C directly on metallic filters. An oxidation of SMF followed by a reduction in H2 create surface roughness, leading to a larger area for CNF nucleation. The CNF formation mechanism includes several steps: it starts with carbon deposition on metallic surface followed by its diffusion into the metal leading to carbides formation. When the limit of carbon solubility is attained, a layer of carbon is formed on the surface of metallic fibers. High tension within the bulk metal leads to carbide dissociation and by phase separation to graphite formation, which pushes the metallic particles through the carbon layer. Nickel, stainless steel an Inconel (an alloy of mainly nickel, iron and chromium) filters were used. The latter gave the highest uniformity of the carbon nanofibers layer showing an excellent mechanical stability. In order to control carbon deposition on the filters, a formal kinetic analysis of the decomposition reaction was undertaken. Partial orders of 1 for ethane, -2 for hydrogen and an apparent activation energy of 235 kJ/mol were obtained. The observed kinetics suggests strongly that the C – C bond scission is the rate determining step and not carbon diffusion into the metal which is often reported in the literature. The synthesis procedures like time on stream and reaction temperature were optimized: 1 hour of a mixture C2H6:H2:Ar (3:17:80) decomposition over SMFInconel at 655°C lead to ∼6% of carbon, leading to a CNF layer of 1 µm thickness covering the metallic fibers entirely. This material presents a high specific surface area (22.2 m2/g) and a low pressure drop for the gas flowing through. The carbon nanofibers have a diameter between 20 and 50 nm and a crystalline structure with platelets morphology where the graphene layers are stacked one above the other. Their surface is composed almost exclusively of carbon and hydrogen. Amongst the multiple possible applications of this novel composite material, its use as a catalyst support was assessed. Selective hydrogenation of acetylene was carried out over palladium supported on CNF/SMF and compared with commercial supports (ACF, EGF and AGF). The activated carbon fibers cloth (ACF) led to a Pd activity at least twice as E-type glass fibers tissue (EGF) or EGF covered by an alumina layer (AGF). Reaction kinetics was studied for Pd/ACF, leading to acetylene and hydrogen partial orders of -0.5 and 2.4, respectively and apparent activation energy of 50 kJ/mol. The negative partial order for C2H2 suggests high adsorption strength of this compound compared to other reagents on palladium. This particularity allows Pd to be selective. Hydrogenations are known to be structure sensitive. Therefore the catalyst activity for the model reaction depends on Pd particle size. It increases for large particle sizes. The control of this parameter was a priority. Variations of the palladium precursor, of the support and catalyst treatment were carried out. Micro-wave plasma was used since it is fast and has low energy consumption allowing chemically modifying the carbon support surface and activating catalyst after impregnation. This controls not only palladium sintering, but also decomposes tetraaminopalladate more efficiently, resulting in a catalyst activity of one order of magnitude higher. In order to control the palladium deposition on CNF/SMFInconel composite, it is important to have surface functional groups. The activation of carbon nanofibers was carried out with a 4 hours treatment in a boiling aqueous solution of hydrogen peroxide. This led to an amount on surface oxygen containing groups, per mass of carbon, higher than in ACF. Palladium particle size on the composite was controlled by support activation, the use of several metal precursors or different loadings or by a thermal treatment in argon at 500°C. Optimisation of the procedure allowed to obtain in a controlled way an average palladium particle sizes between 3.6 and 25 nm. The activity and selectivity towards ethylene of Pd/CNF/SMFInconel were observed to be higher compared to palladium supported on activated carbon, alumina or barite. Graphitic nature of carbon nanofibers, leading to strong metal-support interaction, was accounted as responsible for these improvements. The high thermal conductivity of the composite CNF/SMF ensured good heat transfer released due to the exothermicity of the reaction and allowed to work close to isothermal conditions in the catalytic bed. Finally it can be concluded, that for the first time carbon nanofibers synthesis was carried out in one step on sintered metal fibers filters, resulting in a novel structured composite material combining different specific properties and having promising potential applications.