ICMCTF2011 Session D2: Coatings for Biomedical Implants

Tuesday, May 3, 2011 8:00 AM in Room Royal Palm 4-6

Tuesday Morning

Time Period TuM Sessions | Abstract Timeline | Topic D Sessions | Time Periods | Topics | ICMCTF2011 Schedule

Start Invited? Item
8:00 AM D2-1 Tribological Behavior of DLC Coated CoCrMo Alloys for Medical Joint Applications
Roland Hauert, U. Müller (Empa, Switzerland); G. Thorwarth (Synthes GmbH, Switzerland); K. Thorwarth, M. Parlinska-Wojtan, C.V. Falub (Empa, Switzerland); C. Voisard (Synthes GmbH, Switzerland); M. Stiefel (Empa, Switzerland)
In artificial joint replacements, especially in metal-on-metal articulating joints, an increasing number of patients is suffering from unwanted body reactions due to metallic wear debris. Therefore a very low wear coating is aimed at in medical applications. Diamond-like carbon (DLC) coatings have been proven to maintain low friction and low wear for billions of high load loading cycles in many technical applications. Attempts to obtain low wear in vivo by coating the articulating surfaces of artificial joints with DLC failed mostly after several years in vivo.

In an articulating joint simulator, we analyzed the wear behavior of DLC coated CoCrMo implant pairs up to 80 million loading cycles in simulated body fluid. The results indicate that low wear and lifetime performance may be obtained in-vivo, whenever the interfaces and interlayers between the coating and the implant are stable under biological conditions. Especially the only a few nm thick carbidic reaction layer between the DLC and the CoCrMo implant has a crucial influence on long term adhesion. We will show an XPS analysis of the stoichiometry of these reactively formed interfaces. The slow advancement of cracks in this carbidic interface layer was controlled by the laws of stress corrosion cracking, in highly stressed coatings when exposed to a corrosive liquid such as body fluid. We will also present analysis of in-vivo failed DLC coated implants and show that the primary cause of failure was mainly a slow corrosive attack of the interlayers by the body fluid.

8:20 AM D2-2 In Situ Fabrication of TiN layer on the Nanostructured Surface of Orthopedic NiTi Alloy
Tao Hu, Shuilin Wu, Jiang Jiang (City University of Hong Kong); Ying Zhao (The University of Hong Kong); Chenglin Chu (Southeast University, China); Paul Chu, Kelvin Yeung (City University of Hong Kong)
Because of the unique shape memory and super-elastic properties, orthopedic NiTi alloy are promising materials in surgical implants. In order to enhance the safety after surgery, the surface of the NiTi alloy is usually coated with a TiN film to enhance the anti-corrosion properties and biocompatibility. However, the film fabricated on NiTi is relatively thin and normally only about several hundred nanometers thick. The thin coating can deteriorate quite fast due to fretting inside the human body thus causing out-leaching of harmful nickel ions into human tissues. In this paper, we report the fabrication of a nanostructured layer on the surface of the NiTi alloy produced by plasma nitriding at 370°C. The experimental results show that nitrogen diffusion is enhanced significantly during this process and a thick TiN layer can be formed on the surface of the NiTi alloy. The corrosion resistance of the NiTi with the thick TiN layer is significantly improved. Inductively-coupled plasma mass spectrometry (ICPMS) reveals that the TiN layer can effectively impede the release of the harmful nickel ions into the simulated physiological solution. In vitro biological tests including MTT and cell spreading further disclose good cytocompatibility on the NiTi alloy with the thick TiN layer.

8:40 AM D2-3 From DLC to Nanocrystalline Carbon Coating for Biomedical Applications
Stanislaw Mitura, Katarzyna Mitura (Koszalin University of Technology, Poland); Piotr Niedzielski, Jacek Grabarczyk (Lodz University of Technology, Poland)

In recent years there has been a great deal of research in many laboratories worldwide on the properties of carbon layers which have shown their potential usefulness in medicine. Various medical implants are covered by carbon coating which creates a barrier between the implant and the tissue environment. Studied of diamondlike (DLC) films have proved that such films show high biocompatibility. The biocompatibility of DLC is due to their chemical stability, biostability, and appropriate mechanical and adhesive characteristics of the implant/layer system.

However DLC are not specially applicable in the medical implants, with blood contact. DLC are generally thought to be chemically inert but their biological activity has also been reported.

So, better results has been reported with nanocrystalline diamond (NCD) coating. In this paper the results of experimental studies of nanocrystalline diamond coatings obtained by a method of RF plasma CVD are presented. Nanocrystalline diamond coatings have a thickness of about micrometer and are composed of diamond. They are created from crystallites of the order of few nanometer in size, so they are referred to as nanocrystalline diamond.

They were reported to decrease the level of induced hemolysis and to inhibit lipid peroxidation in blood plasma. NCD Nanocrystalline Diamond Coating (NCD) was found to have positive effects on cells and tissues in the human organism with little adverse reactions. Antiinflammatory action of NCD has been reported.

At present examinations are assigned to acquiring new properties of NCD through their chemical modification which is creating covalent bond with organic moieties. Comparison of different functional groups obtained nanodiamonds depending on their origin causes their different behaviour in biological environment. Therefore examining functional groups of carbon powders coming from technological various processes, also will be recommended of the ones commercially available, next modifying through Fenton treatment, showing changes of functional groups after the reaction and of changes created after the application in the living cell.

9:20 AM D2-5 Characterization of Drug Distribution in Model Polymer Films using XPS Sputter Depth Profiling
David Surman (Kratos Analytical Inc.); Simon Hutton (Kratos Analytical Ltd., UK); Morgan Alexander, Ali Rafati (University of Nottingham, UK)

The chemistry of the surface and near surface region is well known to control the biocompatibility of materials intended for in-vitro use. The distribution of the active substance within polymer film coatings of drug eluting stents (DES) has been the focus of considerable research as the controlled release of the drug over extended periods is of great importance in the functioning of the device. This work presents x-ray photoelectron spectroscopy (XPS) concentration depth profiles using a cluster ion source of flat film models of DES devices containing a drug and poly(l-lactic acid) (PLA) spun cast onto cleaned silicon wafers. Samples were initially characterised using spectroscopic ellipsometry and determined to be ~100nm thick. XPS sputter profiling using a coronene (C24H12+) primary ion source has provided quantitative elemental distribution as a function of depth through the polymer film whist retaining the chemical information. Results indicate that there is a depletion of codeine from the surface with segregation to the bulk of the sample rather than a uniform distribution of the bulk drug loading for these model systems. Parameters known to affect cluster ion depth profiles of DES model systems, including sample temperature and drug loading within the polymer matrix have been studied.

9:40 AM D2-6 Strength and Fracture Behavior of Hydroxyapatite Coatings
H.S.Tanvir Ahmed, Alan Jankowski (Texas Tech University)
Biocompatible coatings of hydroxyapatite must provide a strong interface between metal alloy implants and the porous surface overcoats required for successful in-growth of bone and tissue. The composite structure must transfer stress during loading that requires an adherent and robust base coating. In this study, hydroxyapatite coatings are sputter deposited onto titanium-coated silicon wafers for an evaluation of strength across a wide range of strain rates, and for assessing the initiation of fatigue fracture from high cycle loading. Our dynamic test procedures take advantage of a nanoanalyzer cantilever probe with a diamond stylus to initiate nanoscratch testing for measuring the change in hardness of the coating over a wide strain-rate range. The use of high strain rates may well simulate the loading conditions found at the interface between implants and hydroxyapatite coatings. Initial results indicate the hardness, hence strength, of the hydroxyapatite coating appear somewhat strain-rate insensitive. A second use of the nanoanalyzer provides a method for detecting the transition from elastic to plastic behavior. In the tapping mode, the vibrating cantilever probe is used to detect a linear elastic response when the probe tip contacts the surface and then resonates with deflection of the test surface. Plastic flow and material failure occur when the depth of the probe is progressed further into the surface. The high frequency of the tip-surface oscillation provides a new means of measuring fatigue failure through the loading-unloading cycles that accompany the resonant tip-surface displacement. Measurements are discussed for the fatigue crack growth rate that is especially useful to evaluate the longevity of the implant-coated component. This work was supported by the J.W. Wright Endowment for Mechanical Engineering at Texas Tech University.
10:00 AM D2-7 Nanomechanical Characterization of Atomic Layer Deposition Coatings for Biomedical Applications
Nicole Bauer (Oregon State University); Mansen Wang (Oregon Health and Science University); Sean Smith (Oregon State University); John Mitchell (Oregon Health and Science University); John Conley, Jr. (Oregon State University)

Atomic Layer Deposition (ALD) is a promising technique for the production of biologically safe, wear resistant and corrosion protective coatings for dental and orthopedic applications. In this work, we investigate the impact of coating thickness and surface preparation on the hardness (H), elastic modulus (E), wear resistance, and delamination of ALD Al2O3 films.

Al2O3 was deposited via ALD at 300°C using Al(CH3)3 and H2O. 200 nm, 600 nm, and 1000 nm thick Al2O3 films were coated on polished 305 stainless steel (SS) substrates. Prior to deposition, SS substrates were cleaned using one of three methods: i) sonication in acetone, isopropyl alcohol and deionized water (AID), ii) AID followed by argon plasma treatment, iii) AID followed by oxygen plasma treatment. Nanowear, nanoscratch, and nanoindentation testing were performed using a Hysitron UBI-1 nanomechanical test system. A Berkovich diamond tip was used for nanoindentation testing to calculate the average H and E. A conical diamond tip was used to perform scratch testing in order to determine the delamination force and coefficient of friction values. The same conical diamond tip was also used for wear testing.

Nanoscratch testing and nanowear testing indicates excellent adhesion –Al2O3 films do not delaminate even when penetration depth is beyond the film thickness. Nanoindentation results indicate that the H and E of coated substrates are higher than that of the uncoated substrates. In addition, H and E exhibit a trend of modulus and hardness changing from bulk Al2O3 values to bulk stainless steel values with increasing penetration depth. Nanowear testing demonstrates that ALD Al2O3 films offer effective protection of the SS substrate. Although no distinguishable difference in the wear resistance was observed due to plasma treatment, films of increasing thickness exhibit greater resistance to wear due to reduced coefficient of friction.

In conclusion, we find that ALD exhibits great promise for protective coating of dental and orthopedic devices.

10:20 AM D2-8 Ellipsometric Study of Protein Adsorption onto Biocompatible Coatings
Phaedra Silva-Bermudez, Sandra Rodil (Universidad Nacional Autonoma de Mexico)

Nowadays, medical implants are widely used to repair or replace damaged organs or parts of the human body, improving people’s quality of life or even preserving life. In order to develop new medical implants and to improve the existing ones, it is necessary to develop novel biomaterials. One strategy to develop new biomaterials is to design the bulk material to fulfill the required properties for the implant’s performance and then tailor its surface properties towards biocompatibility by coating it with an adequate thin film.

Whenever a material comes in contact with blood or physiological fluids, as it is upon implantation, a cascade of biological events is triggered; the right development of this cascade of events determines the material’s biocompatibility. One of the first biological events to occur is the adsorption of a layer of proteins onto the material’s surface. This protein layer mediates the subsequent biological events such as cell adhesion. Cells adhere preferentially to specific proteins in specific conformations; thus, the composition and the conformation of the protein layer is a key factor dictating whether the material is biocompatible or not. Due to the importance of protein adsorption to define the biocompatibility of a material, it is essential to develop a fundamental understanding of protein-surfaces interactions in order to design novel and successful biocompatible coatings. Transition metal oxide thin films can be considered as promising biocompatible coatings, based on the successful biocompatibility displayed by TiO2 and the good mechanical, corrosion properties and bioinert response displayed by transition metal oxides.

To evaluate sputtered deposited TiOx, TaOx, NbOx and ZrOx thin films as biocompatible coatings, the in-situ adsorption of albumin, fibrinogen and collagen onto these films was studied by ellipsometry. Protein adsorption onto solid surfaces is affected by the physicochemical properties of the surface; therefore the chemical composition (X-ray photoelectron spectroscopy), wettability and surface energy (contact angle) and roughness and thickness (profilometry) of the thin films were characterized in order to identify any possible relation between these properties and the protein adsorption process. The results showed that for each protein, there is different adsorption kinetics depending on the material, clearly observed by the changes in the ellipsometer spectra. Moreover, the surface mass density of the protein layer, calculated from the fitting of the spectroscopic ellipsometer spectra, was observed to increase with both the average roughness (Rq) of the surface and the polar component of the surface energy.

10:40 AM D2-9 Large-Scale Synthesis of Hierarchical Titanate Spheres as Cell Interface on Titanium Alloys for Bone Tissue Regeneration
Shuilin Wu (City University of Hong Kong); Xiangmei LIU (Hubei University, China); Kelvin Yeung (City University of Hong Kong); Zengfeng Di (Chinese Academy of Sciences (CAS), China); Tao Hu (City University of Hong Kong); Zushun Xu (Hubei University, China); Jonathan Chung, Paul Chu (City University of Hong Kong)
Hierarchical titanate microspheres assembled by one-dimensional nanosheets grow naturally on titanium plate during a simple hydrothermal process. The effects of this new interface on the adhesion of endothelial and osteoblast cells are investigated systematically in this study. These hierarchical microspheres significantly promote endothelial cell adhesion and proliferation of osteoblasts. In addition, this new surface enables much faster mineralization of the adhered osteoblasts as well as formation of two types of major proteins in the bone matrix, namely osteocalcin (OC) and type I collagen (Col I). Our results show that these hierarchical titanate microspheres not only enhance the cytocompatibility for both endothelial and bone cells, but also support fast functionalization of bone cells. Therefore, the large-scale synthesis of hierarchical titanate microspheres which form a natural bone cell interface on titanium biomedical implants is very promising in clinical applications.
Time Period TuM Sessions | Abstract Timeline | Topic D Sessions | Time Periods | Topics | ICMCTF2011 Schedule