ICMCTF2012 Session D3-1: Coatings for Mitigating Bio-Corrosion, Tribo-Corrosion and Bio-Fouling

Monday, April 23, 2012 1:30 PM in Room Sunset

Monday Afternoon

Time Period MoA Sessions | Abstract Timeline | Topic D Sessions | Time Periods | Topics | ICMCTF2012 Schedule

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1:30 PM D3-1-1 Significance of Tribocorrosion and Bio-Tribocorrosion in the Oral Environment: The Case of Dental Implants
Luis Augusto Rocha (Universidade do Minho, Departamento de Engenharia Mecânica, Campus de Azurém, Portugal)

Tribocorrosion covers the material degradation process resulting from the combined interaction of wear and corrosion phenomena on surfaces subjected to a relative contact movement. Bio-tribocorrosion is the designation used to describe the tribocorrosion behavior of materials in contact with biological environments, as it happens in dental implants.

In fact, dental implants are under a complex congregation of mechanical solicitations and chemical aggressive substances, which can change considerably in magnitude or nature over the day and between individuals. Moreover, dental implants have a strong interaction with cells (soft and hard tissue cells and/or microorganisms) resulting in the local modification of the surrounding environment, both from the chemical and mechanical points of view. For instance, while the adhesion of bone cells to the material is desirable to provide osseointegration, colonization by microbes and the consequent formation of biofilms should be avoided. Surface modification routes are being investigated in order to provide multifunctional properties to the surface of dental implants.

In this work, an overview of the current knowledge of the bio-tribocorrosion mechanisms of Ti alloys used in dental implants will be presented. The effects of biofilms or cultured osteoblastic cells on the bio-tribocorrosion response will be addressed. Special focus will be given to surface modifications techniques which presently appears as promising to provide a good combination of biological and bio-tribocorrosion responses.

2:10 PM D3-1-3 Surface modification using PVD to apply silver-copper-mixed layers
Gaby Gotzmann, Christiane Wetzel (Fraunhofer Institut für Elektronenstrahl- und Plasmatechnik, Medizinische Applikationen, Germany); Lars Achenbach, Nurdan Özkucur, Richard Funk (Medizinische Fakultät, Institut für Anatomie, TU Dresden, Germany); Carsten Werner (Leibniz-Institut für Polymerforschung Dresden e.V.,Research Division Biofunctional Polymer Materials, Germany)
At any time, over 1.4 million people worldwide suffer from infectious complications acquired in hospital –so called nosocomial infections. The most frequent nosocomial infections are infections of surgical wounds, urinary tract infections and lower respiratory tract infections /i/. The resulting health care costs just concerning America rise up to almost 2 billion dollar per year /ii/. With the emergence and increase of microbial organisms resistant to multiple antibiotics, and the continuing emphasis on health-care costs, medical research focuses on the development of new, effective antimicrobial reagents for treatment and prevention of infections. This led to the resurgence in the use of silver based antiseptics. The use of silver as an antimicrobial material is known since antiquity. The combination of silver with other antimicrobial active elements –e.g. copper- might even increase the effectiveness. Complementing silver with copper announces decreased probabilities concerning cytotoxic side effects and improved economic application of the used elements. Physical vapor deposition technology was used for surface modification of polyurethane which constitutes a representative for one of the most used materials in medical devices besides stainless steel. Several layer combinations of silver and/or copper were applied with a final layer thickness of 50 nm. Amounts of silver and copper in the layer composition were determined using SEM/EDX. Energetic surface characteristics and wetting behavior were examined via contact angle measurement. Furthermore also antimicrobial effectiveness was tested using recognized microbiological methods and the model organism Escherichia coli K12. The investigations focused on the inhibiting influence of the obtained layers on microbial growth kinetics and possible synergistic effects. In addition cell biological experiments were accomplished to determine cell reaction under direct and indirect contact with the silver-copper layers. The results of this work are the basis to use PVD technology in order to apply antimicrobial coatings – here silver and copper mixtures – for medical-technical applications. Parameters can be adapted specific for every customer and application respectively in order to help you to extend and secure your lead in the market. i World Health Organization, Department of Communicable Disease, Surveillance and Response: Prevention of hospital-acquired infections, A practical guide, 2nd edition; WHO/CDS/CSR/EPH/2002.12 ii 2011 Health Grades Inc: Statistics about Nosocomial infection, http://www.rightdiagnosis.com/n/nosocomial_infections/stats.htm , Last Update: 23 August, 2011 (5:16
2:30 PM D3-1-4 Studies on Corrosion and Tribocorrosion Behaviour of Electrodeposited CoW-WC Nanocomposites
S.K. Ghosh (BARC, India); Jean-Pierre Celis (KUL, Belgium)

Research for alternatives to electroplated hard chromium coatings is continued because of their tremendous environmental and health hazard concern. Among the various possibilities, recently, electroplated Co-W alloys show promising results like abrasive wear and corrosion resistance close to and even better than electroplated hard chromium. In the present study, the Co-W alloy matrix is further strengthened by incorporating nano-size WC particle via electrochemical codeposition technique. The matrix cobalt helps in binding the WC particles and in return particles strengthen the matrix along with host tungsten as alloy element. In order to understand corrosion resistance of these alloys, potentiodynamic polarization was carried out in 0.5M NaCl solution at room temperature and compared with similar composition CoW alloys. Indeed, it was found that nano-size WC particle helps in improving the corrosion resistance of the composites. The differences in corrosion behaviour were understood by analyzing the corroded surface morphology and composition analysis.

Further importance has been given on corrosion behaviour under mechanical loading conditions (known as tribocorrosion) in the same solution to extend the possibility of industrial applications of these coatings. Under mechanical loading and unloading conditions, open-circuit potential (OCP) of a few coatings was measured in order to estimate the material loss under mechano-chemical environment. In this presentation, details of tribocorrosion of these coatings will be discussed correlating with corroded wear scar morphology.

2:50 PM D3-1-5 An Electrochemical Investigation of TMJ Implant Metal Alloys in a Synovial Fluid-Like Environment: The influence of pH variation
Dmitry Royhman (University of Illinois at Chicago, College of Dentistry, US); Rashmi Radhakrishnan, Mathew Mathew, Markus Wimmer (Rush University Medical Center, US); Cortino Sukotjo (University of Illinois at Chicago, College of Dentistry, US)
Temporomandibular Joint (TMJ) disorder affects 30 million Americans, with approximately 1 million new patients diagnosed each year. These pathologic conditions may require reconstruction with total joint prosthesis (TMJ implant) for better treatment prognosis. A total TMJ implant is a metal-on-metal joint, usually made of titanium, cobalt-chromium, or combination of both. In the body environment, the TMJ implant is exposed to variable corrosive conditions from the electrolytic environment, as well as the galvanic effect between the different metals. The primary reason for implant rejection is breakdown and corrosion. Corrosion can severely limit the strength and lifespan of the implant, leading to implant fracture and adverse physiological effects. The objective of this study was to examine the effect of different levels of pH of BCS under simulated physiological conditions on the corrosion behavior of commonly used TMJ implant metals. Corrosion behavior was evaluated using standard electrochemical corrosion techniques and galvanic corrosion techniques. Standard electrochemical corrosion tests were run using a 3-electrode cell as a function of metal type (CoCrMo and Ti6Al4V) and pH (3.0, 4.5, 6.0, and 7.6). Evaluation parameters included: Open Circuit Potential, EIS parameters (Rp and Cp), and Cyclic Polarization parameters (Ecorr, Icorr, and Ipass). Galvanic corrosion tests were run using a 3-electrode cell with Ti6Al4V as the working electrode, CoCrMo as a counter electrode, and a saturated calomel electrode (SCE) as the reference electrode (n=3). Data was evaluated using Two-way ANOVA, Tuckey’s post hoc analysis, and two-sample independent t-test (p=0.05). The metal surfaces were characterized using white-light-interferometry microscopy and scanning electron microscopy (SEM). The cyclic polarization scan showed that Ti6AL4V had an enhanced, stable, passive layer growth and a better corrosion resistance than CoCrMo. EIS measurements indicated that Rp was inversely related to increased pH. Initial galvanic corrosion measurements exhibit the noble electrochemical behavior of Ti6Al4V. SEM and white-light-interferometry images demonstrate a higher increase in surface roughness (Ra) after corrosion in CoCrMo. We concluded that acidity in BCS accelerated the ion exchange between the Metal-electrolyte interface in both metal types and that Ti6Al4V shows better corrosion behavior than CoCrMo. Additionally, corrosion kinetics are influenced by the potential corrosion inhibition properties of the protein content of the surrounding fluid. Further studies are in progress to generate a better understanding of the transitions in the corrosion kinetics due to these proteins.
3:10 PM D3-1-7 Fretting corrosion with proteins: the role of organic coating about the synergistic mechanisms
Jean Geringer, Julie Pellier, Bernard Forest (ENSM-SE, France); Digby Macdonald (CEST-PSU, US)

Fretting corrosion is one of the most deleterious mechanisms for the degradation of metallic biomaterials, especially in the orthopedic field. Around 1.5 million of hip prostheses are implanted worldwide. This work is dedicated to study the synergistic effect of proteins and ions concentration on the wear of stainless steel, 316L, against a polymer sample under fretting-corrosion conditions.

A specific device allows reproducing fretting corrosion, i.e. relative displacements of microns between materials in contact. In order to compare with previous investigations, the amplitude was equal to ± 40 µm with sinusoid dal amplitude. The duration of each test was 14400 s, 4 hours.

The 316L sample size was the same for all samples. 3D roughness of 316L, Ra (3D), was 10 ± 2 nm. PMMA (PolyMethyl Methacrylate) is cylindrical with a roughness of 35 ± 5 nm. 4 solutions of NaCl were selected in order to study the effect of the ionic strength: 10-3 mol.L-1, 10-2 mol.L-1, 10 -1 mol.L-1 and 1 mol.L-1. Additionally on each solution described previously, concentrations of proteins (pure albumin) were: 0, 1 and 20 g.L-1. Experiments were investigated at temperature of 22 ± 1 °C. The potential was equal to -400 mV/SCE and the current density was measured with a particular attention to the device insulation.

The synergistic formalism is:

W = Wc +Wm + (DWcm + DWmc); W: total wear volume; Wc: wear volume due to corrosion; Wm: wear volume due to mechanics; DWcm: synergistic wear volume, corrosion enhances wear due to mechanic; DWmc: synergistic wear volume, mechanic enhances wear due to corrosion.

As expected, the main wear volume of stainless steel is due the synergistic terms for a salts concentration close to the one of human physiological liquid. 10-1 mol.L-1 is the threshold concentration for increasing wear and the part of the synergy effect. At 10-3 mol.L-1 of NaCl, the content of albumin has no significant impact on the wear volume. For fixed salts concentration higher than the threshold, albumin does not promote the wear of stainless steel surface, it decreases (divided by 3 from 0 g.L-1 to 20 g.L-1). The mechanical wear, calculated at applied potential of -800 mV/SCE, does not change according to the albumin concentration.

The most interesting point is the albumin changes the mode of synergy. At 0 g.L-1 of albumin, the main synergistic term is the influence of mechanics on corrosion, DWmc. On the contrary, at 20 g.L-1, the main synergistic term is the influence of corrosion on mechanics, DWcm. One might suggest albumin promotes the corrosion after mechanical damage of the passive film. However albumin prevents from mechanical degradation.

3:50 PM D3-1-9 Optimisation of Pulsed Bipolar Plasma Electrolytic Oxidation of Magnesium Alloy for Biological Applications
Yonghao Gao, Aleksey Yerokhin, Allan Matthews (University of Sheffield, UK)
Magnesium alloys have been considered as promising biomaterials, although their application in biological area is limited by poor corrosion resistance. Plasma electrolytic oxidation (PEO) has been investigated to solve this problem. Alternating current regimes, for example a pulsed bipolar current (PBC) mode, offer a better control over the PEO process and correspondingly the coatings exhibit higher corrosion resistance compared with those produced in DC mode. Intrinsic problems of the PEO process are associated with low energy efficiency, since significant fraction of current is consumed on collateral electrode processes, such as gas evolution and anodic dissolution of metal substrate. Evaluation of the collateral processes is essential to both understand the coating formation mechanism and optimise the coating process in terms of energy efficiency. In the present study, current efficiency of PBC PEO process is investigated and the corrosion performance of the coatings is also studied. For this purpose, PBC current mode with variable frquency and duty cycle is employed to treat a magnesium alloy in an alkaline electrolyte solution. Gas evolution rate and its composition are determined, together with the amount of substrate material lost to the electrolyte. An online gas flow meter and a residual gas analyser (RGA) equipped with a quadrupole mass spectrometer are utilised. This set-up provides a safe and reliable way to evaluate partial electrode processes during PBC PEO treatment. The corrosion performance of the PEO coated magnesium alloy is tested in a simulated body fluid (SBF) at 37 oC using an electrochemical workstation. Based on the experimental results, current efficiency and bio-corrosion performance of PEO coatings are optimised.
4:10 PM D3-1-10 Micro-textured CoCrMo Alloy for MoM joints: An Electrochemical Investigation
Christopher Nagelli, Mathew Mathew (Rush University Medical Center, US); Robin Pourzal, Felix Liedtke, Alfons Fischer (University of Duisburg-Essen, Germany); Markus Wimmer (Rush University Medical Center, US)

In orthopedics, the use of metal-based alloys is a reoccurring practice because of their biocompatibility, low-wear rates and post-operative stability. However, metal-on-metal (MoM) hip joint bearings endure a constant load during articulation while immersed in synovial fluid. This environment has shown to be detrimental because of leaching metal ions and particulate debris in the neighboring tissue that has lead to implant failure and revision surgery. Currently, MoM joints are facing serious challenges with market usage declining from 35% to less than 10%. Tribochemical reactions potentially generate a type of tribolayer on the surface, which has shown a better electrochemical and tribological behavior. However, this layer is very unstable, nonhomogeneous and patchy in appearance. A defined micro-topography of the surface could be a solution facilitating strong film growth. To address these concerns, the aim of the current work is to investigate electrochemical properties of 5 types of topographies on a CoCrMo alloy surface.

Five different topographies were prepared using electrochemical etching. The topographies were adjusted by applying a different current during the etching process. The textured samples were than compared to a control sample that was polished using a conventional polishing process. Corrosion tests were conducted in an electrochemical cell with bovine calf serum (30 g/L protein) as the electrolyte. A standard corrosion test protocol was used that included monitoring of the open circuit potential for 1 hr and an electrochemical impedance spectroscopy test with a frequency range of 100K Hz to 0.005 Hz. Samples were then polarized during the cyclic polarization test from -0.8 V to -0.8 V with a peak voltage of 1.8 V. The surfaces were then characterized using a white light interferometer and scanning electron microscope.

The surfaces with a micro-topography demonstrated an improved corrosion behavior when compared to the control sample. Texturing the surface results in an even distribution of surface depressions. It appears that this topography enhances the adherence of protein resulting in a decelerated corrosion rate. Thus, a micro-topography of the surface is ideal for creating a heterogeneous proteinaceous layer that is analogous to a tribolayer, which is already reported. To further comprehend the properties of a micro-topography it is essential to expose a tribocorrosive environment, combining the influence of mechanical wear and corrosion. It can be assumed that such topography may reduce the influence of abrasion by particle entrapment and enhances the influence of tribolayer formation resulting in lower wear.

Time Period MoA Sessions | Abstract Timeline | Topic D Sessions | Time Periods | Topics | ICMCTF2012 Schedule