ICMCTF2010 Session H3: Surface Engineering of Coatings: Tribo, Bio and Nano-Corrosion Effects

Wednesday, April 28, 2010 8:00 AM in Room Royal Palm 4-6

Wednesday Morning

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8:00 AM H3-1 Nano-Scale Surface Engineering for Tribological and Biomedical Applications
Min Zou (University of Arkansas)
Surfaces engineered with nano-scale topographies and/or chemistries are finding more and more applications in various fields. For example, they are used to improve tribological properties in micro-electro-mechanical systems (MEMS) and computer hard drives, to facilitate cell adhesion and growth in tissue engineering, and to enhance water-repellency of surfaces for anti-corrosion and self-cleaning applications. Herein we show the application of aluminum-induced crystallization (AIC) of amorphous silicon (a-Si) technique to nanoscale surface-topography-engineering for reducing adhesion and friction forces for tribological applications and for enhancing E. coli cell adhesion on glass substrates in an E. coli-based whole-cell chemical sensor . The AIC of a-Si process involves sequential deposition of a-Si and Al films on a substrate, thermal annealing of the substrate, and etching to remove the excess Al. Traditionally, AIC of a-Si has been studied extensively to produce poly-Si films for electronic and photovoltaic applications, such as thin-film transistors, sensors, solar cells, and display panels; while our efforts have been focusing on fabricating nano-topography-engineered surfaces (NTESs) using rapid AIC of a-Si. Our studies show that nano-engineered surfaces have significantly reduced adhesion and friction forces than smooth surfaces with the same chemistry. NTESs were also found to significantly enhance E. coli cell-to-surface adhesion compared to smooth surfaces. Cell adhesion efficiency was found to be controlled by the texture density of the NTESs.
8:40 AM H3-3 Influence of Rare Earth Element Incorporation on the Behavior of Magnetron Sputtered Al Based Alloys
Juan Creus, Christelle Rebere, Cyril Berziou, Andréa Perez, Sébastien Touzain (Université de la Rochelle, France); Alain Billard (Lermps, Utbm, France)

Aluminum coatings are widely used for the protection of steel structures, but nowadays, structural materials are subjected to more severe conditions combining multi-physical parameters. A reinforcement of the properties of PVD aluminum coatings is necessary to check the new operating conditions of the materials. One problem of aluminum in corrosive media is the susceptibility to localized corrosion, and particularly to pitting corrosion in saline solution that drastically reduces the lifetime of the coatings. So it could be interesting to modify the corrosion mechanism from a localized type to a uniform mode.

Aluminum based alloys were deposited on glass substrates by magnetron sputtering PVD technique. Rare earth (RE) alloying elements (Ce, Y or Gd) were added in order to improve the properties of the aluminum coatings. The influence of the addition of different RE elements is discussed. The incorporation of RE elements has a very limited effect on the mechanical properties. For the 3 RE elements, a shift of the corrosion potential towards more negative values was observed when the content of RE elements increased. Extended immersion tests revealed that the corrosion potential of these alloys slightly evolves towards more positive values due to the formation of a passive film. The composition of this passive film will affect the mechanism of pitting corrosion, that could be less harmful for the lifetime of the Al based coatings.

9:00 AM H3-4 Corrosion Resistance of Amorphous Niobium Oxide Thin Films
Sandra Elizabeth Rodil, Giovanni Ramirez, David Turcio-Ortega, Stephen Muhl (Universidad Nacional Autónoma de México, Mexico); Luis Escobar-Alarcon, Enrique Camps (Instituto Nacional de Investigaciones Nucleares, Mexico)

The evaluation of the corrosion resistance provided by insulating coatings to stainless steel is challenging due to the insulating properties of the coatings. Potentiodynamic studies are possible when the coatings have defects (micro pores) that allows the flow of the carriers (electrons or ions) between the substrate and the electrolyte. However, the interpretation using standard Tafel analysis is not accurate for quantitative evaluation of the corrosion properties. The ac techniques, such as, electrochemical impedance spectroscopy (EIS) provides an appropriated interpretation with detailed information of the processes occurring at both the coating-electrolyte interface and the localized corrosion through the small pores.

Niobium oxide ceramic coatings deposited on medical grade stainless steel, could be used as protective coatings in biomedical applications, such as, orthopaedical or dental implants. As a ceramic, it is a very stable material with good mechanical properties and previous studies have shown that it is not-toxic to human cells and tissues. Niobium oxide might occur in different crystalline phases; Nb2O5, NbO2 and NbO and the production of these phases by physical vapor deposition (PVD) methods require deposition at substrates temperature above 300°C. This will lead to a crystalline but columnar microstructure, as common for PVD coatings, where the inter-columnar space always constitute an open porosity where the electrolyte can reach the substrate with the subsequent failure of the coating. Therefore, in this work, we decide to evaluate the corrosion resistance of amorphous niobium oxide (a-NbOx) films using NaCl 0.89% solution, which are known as simulated biological solutions. The films were deposited by magnetron sputtering on stainless steel (AISI 316L) and the corrosion resistance was evaluated using potentiodynamic, polarization resistance and EIS. The deposition conditions and thicknesses were varied to find the ideal coating that could significantly improve the corrosion resistance of stainless steel to a chloride solution. The results showed that 500 nm constitutes a good thickness where there is no interconnected porosity and therefore the a-NbOx film forms a barrier between the electrolyte and the substrate.

9:20 AM H3-5 Electrochemical Behavior of the TiN Coating for the Orthopedic Applications: Influence of Immersion Time and Protein Content
Mathew Mathew (Rush University Medical Center); R Pourzal (University of Duisburg-Essen, Germany); M McFarland (Acree Technologies Incorporated); NJ Hallab (Rush University); A Fischer (University of Duisburg-Essen, Germany); M.A. Wimmer (Rush University)
Recently, metal-on-metal hip joint implants are regaining attractiveness due to their low wear rate, design flexibility and post-operative stability. Due to this fact, improving the surface properties and cell/metal matrix interactions of the implant metals, through the existing/new coating methods or imposing optimum surface texture are the topical issues in orthopedic implant research. Titanium nitride (TiN) coating is one of the methods to improve the surface hardness and performance of the implant surface. However, biocompatibility and corrosion resistance of such modified surfaces in-vivo provoke concerns.

In this study, the electrochemical behavior of a TiN film deposited by cathodic arc method (substrate: Ti6Al4V) was investigated in bovine calf serum (BCS, protein: 30 g/L) and ringer solution at 37oC. The corrosion behavior was studied by measuring open current potential (OCP) and Potentiodynamic test. Further, the electrochemical behavior was investigated as a function of immersion time (1hr, 15 hrs, 40 hrs, 115 hrs) in both solutions. Electrochemical impedance spectroscopy (EIS) technique was used to characterize the electrochemical double layer and corrosion kinetics. Optical and SEM images were used to characterize the corroded surface. Results indicate that the presence of the protein in the solution increases the possibility of pit formation on the surfaces and may adversely affect the overall corrosion resistance of the TiN coated surface.

9:40 AM H3-6 Surface Nanocrystallization in a NiTi Alloy Subjected to Surface Mechanical Attrition Treatment
Tao Hu (City University of Hong Kong, China); Chenglin Chu (Southeast University, China); Ricky Fu, Paul Chu (City University of Hong Kong, China); Jian Lu (The Hong Kong Polytechnic University, China); Kelvin Yeung (The University of Hong Kong, China)
Among various shape memory alloys, intermetallic NiTi alloy is an important material which has been widely used. Recently, the fabrication of nanocrystalline NiTi alloy has attracted a lot of attention due to both scientific and technological benefits. Several techniques such as high pressure torsion (HPT), equal channel angular pressure (ECAP), and mechanical alloying (MA) have been employed to synthesize nanocrystalline NiTi. However, these techniques can only produce nanocrystalline NiTi specimens with a small size thereby limiting further applications. S urface mechanical attrition treatment (SMAT), which has been successfully applied in synthesis of nanocrystalline metals in many materials systems, has some unique advantages compared to HPT, ECAP and MA. For example, the size of the specimen fabricated by SMAT meets many engineering application requirements. In this work, we utilize SMAT to create a nanocrystallines layer in NiTi alloy. The cross-sectional microstructure of the NiTi alloy processed by SMAT is characterized by X-ray diffraction (XRD), optical microscopy (OM) and transmission electron microscopy (TEM). The results show that SMAT produces nanocrystallines in the surface layer of the NiTi alloy. Besides, a graded microstructure along the cross-sectional depth is created in the NiTi alloy after SMAT due to the gradient evolution of strain and strain rate from the treated surface into the substrate. The results provide useful information pertaining to nanocrystallization of NiTi alloy with the evolution of strain and strain rate.
10:00 AM H3-7 Bio-Corrosion and Cell Culture: Implications in Dentistry and Orthopedics
C. Sukotjo (University of Illinois); M.A. Wimmer (Rush University)

Usage of implants in human body has a long history of more than thousand years, and it is accepted as an effective clinical method, particularly in dentistry and orthopedics. Recently the implant usage is dramatically increased, for example, 500,000 stainless steel cardiac stents are now implanted in the US, every year. In dentistry, implant supported overdenture has been accepted as a standard of care in many countries.

However, in addition to the functional requirement, the nature of implant metals in the body environment always invites some concerns, particularly the issues such as the interactions with adjoining tissues and release of metal ions and its transport to the remote organs. Due to the clear clinical evidences (tumors, hyper sensitivity etc.) of such influence, during last 10 years, many studies were reported on the corrosion behaviour of the implant metals, based on the specific applications and environments, (For example, Cp Ti, in artificial saliva as a function pH). The main challenges in the area of Bio-corrosion is the need of researchers from materials science, physicians, biochemists, electrochemist, mechanical engineers, tribologist and microbiologist and evaluating their new finding in the light of clinical experience and effective practical implementations.

Hence this presentation addresses the progress made in the area of bio-corrosion, specifically, in the dentistry and orthopedics and some insights in methodologies in studying together electrochemistry, surface chemistry and cell culture. The influence of protein content in a biofluids on corrosion kinetics is highlighted. Further, importance of research area called tribocorrosion which simulates natural conditions, such as mastication or artificial joint, where the implants are exposed to movements in the chemical environment is outlined. Keeping this view, Dental school at UIC and Tribology Section, Dept of Orthopedic surgery (RUSH University, Chicago) established a strong research collaboration to address such issues and some recent outcomes and a road map and scope of this research area are included.

10:40 AM H3-10 Comparison of the Properties of Al-Ti and Al-Mg EBPVD Coatings
Andréa Perez (Université de La Rochelle, France); Frederic Sanchette (CEA, France); Alain Billard (Lermps, Utbm, France); Christelle Rébéré, Cyril Berziou, Sébastien Touzain, Juan Creus (Université de la Rochelle, France)

Aluminum based alloys were deposited on glass substrates by electron-beam evaporative PVD technique. Alloying elements (Ti or Mg) were added in order to improve both mechanical and corrosion behaviors of aluminum films. This approach aims to develop sacrificial protection of flat steel products. Since their vapour pressures are different, aluminum and alloying elements were co-evaporated from two separate sources. Different contents of transition metals were examined

The electrochemical characterizations were carried out in saline solution. It is shown that aluminum can be mechanically reinforced with preserving sacrificial behaviors. The evolution of the properties is strongly linked to the nature of the incorporated element. A comparison with a previous study on the electrochemical and mechanical behaviors of Al-Cr and Al-Gd EBPVD coatings will permit to complete the analysis of the influence of the incorporation of transition metal in aluminum.

11:00 AM H3-11 Influence of pH on the Tribocorrosion Nature of the CpTi in an Oral Environment: Mechanisms and Synergism
Savi Abey (University of Illinois); Mathew Mathew, DJ Hall (Rush University Medical Center); NJ Hallab, M.A. Wimmer (Rush University); C. Sukotjo (University of Illinois)
Dental implants have been used in restorative dentistry as a predictable therapy approach to replace missing teeth. Due to its acceptable mechanical properties and minimum inflammatory reaction, titanium is commonly selected for dental implants. However, early failure of some implants invites concerns for long-term survival and the subsequent effects on the patients. A new research area called tribocorrosion, combining the study on wear behavior, i.e. tribology, and its response to the chemical environment, i.e. corrosion, has developed. Applying tribocorrosion principles to dental materials, specifically dental implants, will help manufacturers and practitioners understand product capabilities and limitations prior to use.

In this study, the tribocorrosive nature of titanium (CpTi) was investigated in artificial saliva as a function of pH (3,6,9) and load (20N). The sliding duration (2000 cycles), frequency (1.24 Hz) and load parameters were selected to closely mimic the oral environment and mastication process. The evolution of the current (at potentiostatic condition of Ecorr (E vs SCE)) and friction coefficients were measured during the test. Electrochemical impedance spectroscopy (EIS) measurements were made before and after the sliding (wear test) to comprehend the changes in the corrosion kinetics and surface chemistry. The results indicate that there is a major influence of pH on the tribocorrosion mechanisms and the synergistic interactions of wear and corrosion. Particularly, the high weight loss at pH 6.5 invites some concerns on the implant behavior in a normal oral environment.

11:20 AM H3-12 In-Situ Impedance Spectroscopy Characterisation of Plasma Electrolytic Oxidation Process for Deposition of Ca- and P-Containing Coatings on Ti
Yerokhin Aleksey (University of Sheffield, United Kingdom); Evgeny Parfenov (Ufa State Aviation Technological University, Russia); Allan Matthews (University of Sheffield, United Kingdom)
Plasma electrolytic oxidation (PEO) of Ti currently attracts significant interest in the field of functional coatings, especially for catalytic, photovoltaic and biomedical applications. For the latter purposes, the PEO TiO2 coatings are added with various calcium phosphate compounds that provide intrinsic bioactivity to the coating material. In-situ formation of these compounds is possible only if appropriate electrolyte solutions and current regimes of plasma electrolytic oxidation are carefully selected. Exact mechanisms of coating formation and principles of process control however remain unclear. In this paper, the coating formation processes were studied in-situ using impedance spectroscopy techniques. The main technical challenge of obtaining a frequency response from the high-voltage plasma-assisted electrochemical process was overcome by application of a frequency sweep of bipolar voltage pulses between 20 Hz and 20 kHz. Characteristic frequency bands were identified corresponding to the coating growth under charge transfer and diffusion control. From impedance spectra, the values of charge transfer resistance and barrier layer capacitance were derived and compared to those obtained using ex-situ impedance spectroscopy of resultant coatings. It is shown that under pulsed bipolar conditions of PEO, the critical frequency corresponding to the transition to diffusion control is can be substantially reduced. This indicates that the incorporation of Ca-and P- into PEO coating can be controlled in a wide range of frequencies mainly by electrolyte composition, whereas the current mode can be primarily used to tailor the coating morphology.
11:40 AM H3-13 Tribological Behaivor and Corrosion Performance of Nanocomposite Coating Layer of nc-TiN/a-Si3N4 Deposited by Sputtering on AISI 316L Stainless Steel Duplex for Biomedical Applications
Jose Garcia, Martin Flores (Universidad de Guadalajara, Mexico)
In this work a nanocomposite coating layer of nc-TiN/a-Si3N4, one of promising nitride coatings to extend the life time of mechanical components due to its high hardness value (>40 GPa), were deposited on AISI 316L stainless steel duplex substrate by a DC reactive magnetron sputtering technique. Tribological and corrosive tests were conducted with the purpose of establish the possibilities to use it as a biomaterial in the body, including: X-ray diffraction to analyze the nanostructure of the film, profilometry to analyze the topography of substrates, films and wore Surfaces (tribologicaly tested) , scratch test to evaluate Film adhesion to the substrate and electrochemical technique and scanning electron microscopy (SEM) to evaluate the corrosion susceptibility of the nanocomposite coating. All the results are discussed and compared against the substrate material.
12:00 PM H3-9 Identification of Tribo-Corrosion Regimes for Dental Materials and Coatings
Margaret Stack, C. Hodge (University of Strathclyde, United Kingdom)

In studies of tribo-corrosion, the performance of dental materials is becoming of increasing interest. This is because in oral environments, corrosion, together with wear arising from oral processing, provide a tribo-corrosion environment which can vary significantly in pH, load, and size of wear debris. In such conditions, the performance of materials may be difficult to predict.

In tribo-corrosion, there has been significant research into descriptions of regimes of degradation. More recently the distinctions of wear affected corrosion (“additive behaviour) and “corrosion affected wear (“synergistic behaviour”) have also been made. Such categories enable a mechanistic description to be assigned for the various tribo-corrosion processes.

In this work, the performance of a candidate dental material and a hydroxyapite coating were compared with a reference material-steel- in various micro-abrasion-corrosion environments. The environments included acidic conditions i.e. in orange juice and neutral solutions i.e. milk. Regimes of tribo-corrosion were identified based on the results enabling a new mechanistic description to be defined for dental materials and coatings

Time Period WeM Sessions | Abstract Timeline | Topic H Sessions | Time Periods | Topics | ICMCTF2010 Schedule