ICMCTF2009 Session TS3-2: Bioactive Coatings and Surface Biofunctionalization

Tuesday, April 28, 2009 8:00 AM in Room Sunset

Tuesday Morning

Time Period TuM Sessions | Abstract Timeline | Topic TS3 Sessions | Time Periods | Topics | ICMCTF2009 Schedule

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8:00 AM TS3-2-1 Surface Functionalization of High Strength Biomedical Ceramics
J.R. Piascik (RTI International); J.Y. Thompson (NOVA Southeastern University); E.J. Swift (University of North Carolina at Chapel Hill); S. Grego, B.R. Stoner (RTI International)

There has been much advancement in the development of ceramics for biomedical use, expanding the use of high strength materials (e.g. alumina and zirconia) in varying prosthetic and reconstructive applications. In dentistry, high strength ceramics have become a popular alternative to traditional porcelains, due to their superior fracture resistance and long-term viability. A major clinical problem with the use of indirectly placed alumina and zirconia restorations is the difficulty in achieving adequate bonding with the underlying substrate (tooth structure, implant abutment). Traditional adhesive bonding techniques used with silica-based ceramics like porcelain do not work effectively with these higher strength materials. Initial investigations focused on functionalizing alumina and zirconia surfaces with an ultra-thin Si-based layer (1-25 nm thick) allowing for silane treatments to tether hydro-carbons. These hydro-carbon groups are a common reactant with acrylic poly mers, allowing for strong covalent bonding between prosthesis and the underlying structure. As a proof of concept, several planar test structures, consisting of dental alumina and zirconia, were prepared, treated, and analyzed, before and after Si-O modification, using x-ray photoelectron spectroscopy (XPS). XPS studies indicated that the pretreatment process deposited less than five monolayers of SixOy on the surfaces. A commercially available silane was then applied to the treated surfaces. High resolution core scans of the C(1s) and Si(2p) supports successful chemical bonding of the organo-silane to the Si-O treated surfaces. Mechanical property analysis, consisting of micro-tensile testing of zirconia bonded to a dental composite, revealed that pretreatment of bonding surfaces increased the failure strength over traditional bonding techniques.

Research was supported by NIH/NIDCR DE013511-09 and an internal research grant provided by RTI International.

8:20 AM TS3-2-2 Osteoblast Adhesion to Metal-Oxide Incorporated Diamond-Like Carbon Films
L.K. Randeniya, A. Bendavid, S. Amin, P.J. Martin (CSIRO Materials Science and Engineering, Australia); R. Rohanizadeh (University of Sydney, Australia)
The interaction of osteoblast cells with diamond-like carbon (DLC) films modified by the oxides of Si, Ti, Zr and Hf is investigated. The films were prepared using a pulsed direct-current plasma-activated chemical vapour deposition method. The correlations between cell-attachment properties and the surface energy/chemical composition of the films are discussed. The variations in the mechanical properties (hardness and residual stress) as a function of the concentrations of oxides in the films are presneted. Using these results, the feasibility of these films as coatings for prosthesis in orthopaedic and blood contact applications is discussed.
8:40 AM TS3-2-3 Tribology and Corrosion Behavior of Alpha Alumina-coated Ti-6Al-4V for Surgical Implantation
M.T. Montgomery (University of Arkansas); P. Mohanty (University of Michigan); H.H. Abu-Safe (Lebanese American University, Lebanon); M.H. Gordon (University of Arkansas)

Alpha alumina thin films are excellent candidates for implantation due to the material’s resistance to corrosion, wear, and protein adsorption. Applying such films to a suitable bulk material can be problematic however, as current methods reach high temperatures unsuitable for commonly used alloys or involve undesirable template materials such as chrome.

Thin films of reactively sputtered aluminum oxide were deposited at 480°C on Ti-6Al-4V ELI substrates with no template layer. Process parameters (including magnetron power, substrate biasing, process pressure, oxygen partial pressure, film thickness, and substrate orientation) were varied to investigate the influence of deposition conditions on film quality, crystallography, and mechanical and corrosion behaviors. Film phase has been determined by XRD. Corrosion behavior was assessed using electrochemical impedance experiments. Tribological testing of film hardness and wear resistance supports the XRD resul ts. A detailed discussion of the effect of varying deposition parameters on the properties and performance of the coatings will be presented as well as a comparison to previous literature results.

9:00 AM TS3-2-4 Fabrication of Hierarchical Wrinkled Micro-Pillars using Diamond-Like Carbon Coating
Y. Rahmawan (Seoul National University, Korea); Sk.F. Ahmed (Korea Institute of Science and Technology, Korea); K.J. Jang (Seoul National University, Korea); K.S. Kim (Brown University); M.W. Moon, K.R. Lee (Korea Institute of Science and Technology, Korea); K.Y. Suh (Seoul National University, Korea)

Superhydrophobic surfaces can be utilized to prevent cells proliferation that causes most of failures in biomedical devices. We have shown novel method to fabricate superhydrophobic surfaces based on 3-D hierarchical wrinkle structures combined with the replica molding to make the micro-scale pillar array on PDMS as the soft base material, covered by nanoscale wrinkle patterns formed with hydrophobic diamond-like carbon (DLC) using RF-CVD to make nanometer scale roughness. Nanoscale wrinkle patterns were controlled by varying the thickness of film, causing different pattern width.

Superhydrophobicity of the surfaces can be achieved when we have 3-D hierarchical structures on pillars with spacing ratio of 1 to 4. It was found that theoretical wetting analysis was well matched the experimental results that the wetting states are Cassie and Cassie for microscale roughness and nanoscale roughness, respectively (Cm-Cn) at spacing ratio of 1 to 4, while transformed into Wenzel and Wenzel (Wm-Wn) at spacing ratio higher than 5.

The superhydrophobic surface with hierarchical wrinkled patterns was applied for the cell template with the Calf Pulmonary Artery Endothelial (CPAE) cells. It was observed that the CPAE cells were very difficult to adhere to the 3-D wrinkled surface and the rejection of filopodia extension was observed on the protrusion of nanoscale wrinkles. Further more, as the spacing between the pillars close to 1, the filopodia spreading was highly hindered by the small focal adhesion point of the cells on hierarchical structures since the filopodia spread from top to top of the pillars. This limited focal point adhesion of the cells to superhydrophobic surfaces would prevent the growth and proliferation.

9:20 AM TS3-2-5 Anti-Microbial Properties of Silver Modified Amorphous Carbon Films
A Almaguer-Flores (Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Mexico); R Olivares-Navarrete (Department of Biomedical Engineering, Georgia Institute of Technology); L.A. Ximénez-Fyvie, O. Garcia, S.E. Rodil (Universidad Nacional Autónoma de México)
Silver has been used as an anti-microbial material since historic times. It is well known that microbial infection on implant surfaces has a strong influence on healing and long-term outcome of dental implants. During the last year we have been investigating amorphous carbon (a-C) films as a surface modification for metallic dental implants, but the antimicrobial properties of the a-C films evaluated using oral bacteria and compared to medical grade stainless steel (SS) were similar. Therefore, in this work, we tested if by addition of silver we could improved the anti-microbial properties of amorphous carbon films. The a-C:Ag films were deposited by co-sputtering using a graphite target (10 cm diameter) with an small piece (1 cm2) of pure silver and under an Argon plasma. Bacterial adhesion on the a-C, a-C:Ag, the SS substrates and samples of Ti6Al4V (which is the standard implant material) was evaluated during 24 hrs, 3 and 7 days of incubation. We used nine oral bacteria strains: Actinobacillus actinomycetemcomitans serotype b, Actinomyces israelii, Campylobacter rectus, Eikenella corrodens, Fusobacterium nucleatum ss nucleatum, Peptostreptococcus micros, Porphyromonas gingivalis, Prevotella intermedia and Streptococcus sanguinis. After anaerobic incubation, the total number of colony forming units (CFUs) was counted and the surfaces were observed under the scanning electron microscope (SEM). The effect of including silver on the a-C films was characterized by Raman, X-ray Diffraction, Energy Dispersive spectroscopy, Atomic Force Microscopy and SEM. The results showed that under certain deposition conditions the films have silver nanoparticles (40-60 nm) uniformly distributed in the carbon matrix. The silver was crystalline with a maximum composition around 10 at%. Concerning the antimicrobial properties we did not observe a great effect of the silver particles on the CFU’s after 24 hrs and 3 days of incubation, but small reduction was observed after 6 days. Nevertheless, in this study we showed that the a-C surface has better anti-microbial properties than the Ti6Al4V.
9:40 AM TS3-2-6 Rapid Antimicrobial Susceptibility Testing of Escherichia Coli and Staphylococcus Aureus by Using the Cr-Cu-N Nanocomposite Thin films with Gradient Copper Content
Y.-J. Chang, K.-J. Weng, J.-S. Lu, J.-T. Chen, J.-L. Li, J.-W. Lee (Tungnan University, Taiwan)
The E-test is an antimicrobial agent gradient-coated plastic test strip which allows for quantitative antimicrobial susceptibility testing, or Minimum Inhibitory Concentration (MIC), on agar media. In this study, The Cr-Cu-N nanocomposite thin films were deposited on SUS304 substrates with different Cu contents using bipolar asymmetry pulsed DC reactive magnetron sputtering system. The thin film with gradient copper content ranging from 3.5 to 20.0 at.% was achieved by adjusting the distance between the Cu/Cr targets and substrates. The antibacterial tests of thin films containing different copper content were performed to evaluate the bactericidal ability against both E. coli and S. aureus. A film attachment method (modified JIS Z 2801:2000) was adopted for evaluating the antibacterial activity of the specimens with uniform Cu contents. The MICs were estimated after 24 hr incubation on the measurement of the elliptical zone of growth inhibition due to the copper ion wh ich diffused from the coupons with gradient copper content. It was observed that the interspaces of the antibacterial zones are almost proportional to the antibacterial rates under different copper content of thin films. The nanocomposite thin films with gradient copper content produced in this work are useful for rapid screening antimicrobial susceptibility testing.
10:00 AM TS3-2-7 Electrochemical Characterization of Biocompatible TiOx and NbOx Films
P.N. Rojas, S.E. Rodil, H. Arzate, S. Muhl (Universidad Nacional Autónoma de México)
The corrosion resistance of materials in the body fluids is one essential factor to determine the lifetime of medical implants. Therefore, it is of great relevance to understand the interface process occurring when a surface is exposed to a body fluid, which can be studied by impedance spectroscopy. Titanium and Niobium oxide films were deposited on medical grade stainless steel using a magnetron sputtering system working. These films were evaluated using Potentiodynamic polarization (PP) in 0.89% NaCl (7.4 pH) in order to determine the conditions that lead to the best corrosion resistance. The biocompatibility of best films was evaluated by adhesion and viability/proliferation assays using human cells. Moreover, the long-time stability of the films was evaluated by electrochemical impedance spectroscopy (EIS) as a function of time up to 500 hrs using three different simulated body fluids; the NaCl solution and Hartman (Ringer’s + Lactate) and Gey’s (Ringer’s + Phosphates + Glucose) solution, in order to correlate their protective properties against different composition of electrolytes. The results indicated that there are strong differences according to the chemical composition of the solution and different electrochemical response can be obtained for the same coating, just by changing the solution. For example, NbOx showed a better resistance than the TiOx films in the Hartam’s solution but it failed when Gey’s solution was used. Meanwhile TiOx showed a well passivated response for both NaCl and Gey’s solution. The EIS spectra were analyzed using circuit models in order to understand the different kinetic and interfacial processes occurring for each film and solution.
10:20 AM TS3-2-8 Structural Characterisation of Multifunctional Biocompatible Ti(CON) Based Boatings
S. Ribeiro, N. Jordão (Universidade do Minho, Portugal); A.P. Piedade (Grupo de Materials, Portugal); M. Henriques, R. Oliveira (Universidade do Minho, Portugal); R. Escobar-Galindo (Instituto de Ciencia de Materiales de Madrid (ICMM -CSIC), Spain); S. Carvalho (Universidade do Minho, Portugal)
Application of coatings in the biomedical engineering field represents an attractive challenge. Implant failure is a huge problem for both the patient and the government, once it involves repeated surgeries and high costs. This failure can be attributed to excessive wear and wear debris and also to microbial infection. Toxic effects possibly caused by excess of metal ion release during corrosion process in the physiological environment, it is still not well known. For this purpose Ag-TiCN films were deposited by DC unbalanced reactive magnetron sputtering by changing the synthesis conditions. Through variation of composition different coatings have been attained. Rutherford backscattering (RBS) and Glow Discharge Optical Emission Spectroscopy (GDOES) were used in order to obtain the chemical composition of as-deposited coatings. The microstructure and phase composition of coatings were studied by means of X-ray diffraction (XRD). The aim of this work is to compare surfa ce chemical and morphological changes introduced by commonly used simulated physiological conditions during corrosion process. Surface analytical techniques such as Auger electron spectroscopy (AES) combined with Scanning electron microscopy (SEM) examinations will provide details about the chemical composition as well as morphology of the surface samples. Observations of metal ion release from different biomaterials will be achieved by atomic absorption. Particular attention is paid to possible surface chemical and morphological changes which may be decisive for their interactions with animal cells.
10:40 AM TS3-2-9 Preparation of Plasma-Polymerized Para-xylene as an Alternative to Parylene Coating for Biomedical Surface Modification
C.-M. Chou (Feng Chia University; Taichung Veterans General Hospital, Taiwan); K.-C. Hsieh (Feng Chia University, Taiwan, R.O.C.); C.-J. Chung (Central Taiwan University of Science and Technology, Taiwan); J.-L. He (Feng Chia University, Taiwan)

Parylene (or poly-para-xylene) coating known to be a transparent, uniform and effective barrier. There are however some drawbacks, including expensive starting material, high thermal energy consumption for monomer generation, high vacuum requirement and low growth rate. In this study, low-cost para-xylene was used as the starting material to form plasma-polymerized films. A pulsed-dc plasma power supply was used and the deposits were examined their microstructure, mechanical properties and fibroblast cytotoxicity.

Experimental results reveal that the coatings present an amorphous structure with their deposition rate widely ranging from 50 to 480 nm/h, depending on the pulse frequency (ωp) of the input power and argon flow rate (fAr, para-xylene monomer carrier gas). At high fAr and low ωp, the plasma-polymerized para-xylene (PPX) films exhibit alkane and alkene features, indicating a more organic character. In contrast, the films obtained at low fAr and high ωp present inorganic features. For its mechanical properties, a pencil hardness of 7H-8H of the coated specimen is higher than that of the conventional parylene coating, and the film adhesion graded at 4B determined using the cross-cut test is similar to that of the conventional parylene coating. The water contact angle of PPX films was measured and ranged from 60° to 85°, which is more hydrophilic than the conventional parylene coating. Cell cultures on PPX deposited specimens present a higher cell count than the parylene deposited film. The PPX films deposited at high ωp and low fAr exhibit a lower water contact angle (hydrophilic), which accounts for its better cell compatibility. These quantitative indications imply that the plasma-polymerized para-xylene is a possible alternative to the conventional parylene coating for biomedical device surface modification.

11:00 AM TS3-2-10 Micro-arc Oxidation of β Titanium Alloy: Structural Characterization and Osteoblast Compatibility
H.-T. Chen (Feng Chia University; China Medical University Hospital, Taiwan); C.-H. Hsiao, H.-Y. Long (Feng Chia University, Taiwan); C.-J. Chung (Central Taiwan University of Science and Technology, R.O.C.); C.-H. Tang (China Medical University, Taiwan); K.-C. Chen, J.-L. He (Feng Chia University, Taiwan)

The β-titanium alloys have recently become important in bone implant applications. In this study, micro-arc oxidation (MAO) was used to modify the surface of β-titanium alloy (Ti-13Cr-3Al-1Fe) using NaH2PO4 solution as an electrolyte. The microstructure of the oxidized layer as a function of the applied voltage and treatment time were investigated. The cellular adhesion, proliferation and alkaline phosphatase (ALP) activity of MC3T3-E1 pre-osteoblast were measured to reveal the cell compatibility of the treated specimens.

The experimental results show that micro-structure of the oxidized layer can be greatly affected by the discharge voltage and treatment time during MAO treatment as α-titanium metal and α+β titanium are. The oxidized layer can gradually increase its thickness, pore size and surface roughness as a function of the discharge voltage and treatment time, which at the same time increases the rutile phase constituent. The osteoblast cell compatibility presented by the treated specimens is increased but less sensitive to the process parameters, even though the associated difference in morphology and crystalline form are found to be tremendous.

11:20 AM TS3-2-11 Nanoindentation and Corrosion Studies of TiN/NiTi Thin Films for Biomedical Applications
D. Kaur, A. Kumar (Indian Institute of Technology Roorkee, India)
Proper passivation to prevent surface layer degradation and nickel releasing into the environment has been considered crucial for the medical applications of NiTi based shape memory alloys (SMA). To apply NiTi surgical devices in the human body, the surface properties and corrosion resistance are important material characteristics. Therefore, a stable, biocompatible and corrosion resistant passive layer is required.The present study explored the deposition and effect of nanocrystalline TiN protective layer on NiTi thin films prepared by dc magnetron sputtering to improve the surface and mechanical properties of SMA thin films.The structural, electrical, and mechanical studies were performed on both uncoated and TiN coated NiTi films and the results were compared. The size and preferred orientation of grains in the TiN passivation layer were observed to have a significant influence on the properties of TiN/NiTi heterostructure. Nanoindentation studies were performed at t emperatures of 297K, 323K, and 380K to determine the hardness and reduced modulus. Topographical in-situ images taken on the surface of pure NiTi and TiN coated NiTi showed an improvement in surface roughness after passivation coating. The investigations showed that TiN (200)/NiTi films exhibit high hardness, high elastic modulus, and better corrosion resistance as compared to pure NiTi and TiN (111)/NiTi films. In addition the presence of TiN (200) improves the top surface quality of NiTi films while retaining the phase transformation effect.
Time Period TuM Sessions | Abstract Timeline | Topic TS3 Sessions | Time Periods | Topics | ICMCTF2009 Schedule