ICMCTF2015 Session DP: Symposium D Poster Session

Thursday, April 23, 2015 5:00 PM in Room Grand Hall

Thursday Afternoon

Time Period ThP Sessions | Topic D Sessions | Time Periods | Topics | ICMCTF2015 Schedule

DP-4 Antibacterial Activity and Cell Compatibility of TiZrN, TiZrCN, and TiZr-amorphous Carbon Coatings
Heng-Li Huang (China Medical University, Taiwan); Yin-Yu Chang, Jia-Xu Liu (National Formosa University, Taiwan); Ming-Tzu Tsai (Hungkuang University, Taiwan); Chih-Ho Lai (China Medical University, Taiwan)
Both titanium (Ti) and Zirconium (Zr) has been considered as an excellent biomaterial to the application of medial industry. Both Ti and Zr are so popular that Ti-Zr alloy dental implant has been applied commercially in clinical use. However, the effect of Ti-Zr films with different chemical contents (e.g. nitride (N) and carbon (C )) on the biocompatibility and antibacterial has not been investigated and remain to be determined. Therefore, the purpose of this study was to verify the antibacterial performance, and cell compatibility and proliferation of Ti –Zr–N, Ti–Zr–C–N, and TiZr–amorphous carbon coatings with different chemical contents on commercially pure Ti plates. A cathodic-arc evaporation system with plasma enhanced duct equipment was used for the deposition of TiZrN , TiZrCN and TiZr–amorphous carbon coatings. Reactive gases (N2 and C2H2) activated by the titanium and zirconium plasma in the evaporation process was used to deposit the TiZrCN and TiZr–amorphous carbon coatings with different carbon and nitrogen contents. The composition of the deposited coatings was measured by an energy dispersive spectrometer (EDS). The crystalline structures and bonding states of coatings were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). A surface profilometer was used to measure the surface roughness of the coatings. Potential resistance tests were used to measure the corrosion resistance. The microbial activity of the films was evaluated against Staphylococcus aureus (Gram-positive bacteria) and Actinobacillus actinomycetemcomitans( Gram-negative bacteria ) by in vitro anti-bacterial analysis of a fluorescence staining method employing Syto9 and bacterial-viability test on agar plate. The cell compatibility and morphology related to cell-line human skin fibroblast cells (CCD-966SK) on the coated samples were also determined by using the MTT assay, reverse transcriptase–polymerase chain reaction (RT-PCR), and scanning electron microscopy (SEM). The results suggested that the antibacterial performance of TiZrCN films is superior to TiZrN and TiZr–amorphous carbon coatings whilst maintaining compatible human soft-tissue compatibility.
DP-5 Osteogenesis Ability of Biomimetic Modified 3Y-TZP Ceramic Using Chemical Treatment
Shih-Kuang Hsu (Central Taiwan University of Science and Technology, Taiwan); Pai-Ling Chang (Taoyuan General Hospital, Taiwan); Wen-Fu Ho, Hsueh-Chuan Hsu, Huei-Jyuan Liao, Shih-Ching Wu (Central Taiwan University of Science and Technology, Taiwan)

The dental implant is now a topical subject for the dental community because of the aspect of natural tooth retention. The use of zirconia ceramic as implant material would be a solution for the aesthetic point of view. Zirconia ceramic possesses a good chemical and dimensional stability, and a high strength and fracture toughness. Because of the bioinert property, how to improve osteogenesis ability becomes the important issue for using zirconia implants in dentistry. In this study, RGD-peptide derived from extracellular matrix proteins was employed to modify the surface of yttria-tetragonal zirconia polycrystal (3Y-TZP) to promote cell adhesion.

First, the surface of 3Y-TZP ceramic specimens was modified using chemical treatment with aqueous solutions of H3PO4, CH3COOH, and NaOH, for the formation of Zr-OH surface functional groups. The topographies of modified 3Y-TZP specimens were analyzed by contact angle, XRD, FTIR, AFM and FE-SEM. The mechanical properties were evaluated by Vickers hardness and three point bending strength.

The RGD-peptide was then immobilized on the surface of the 3Y-TZP through silanization method, with covalent bonding via the Zr-OH surface functional groups. The RGD-immobilized 3Y-TZP was characterized by FTIR and AFM, and then was cocultured with MG-63 osteoblast cells for the biocompatibility assay. The cell morphology and proliferation were evaluated by SEM, WST-1 and ALP activity assay.

From this study, the RGD-peptide can successfully be grafted onto the chemical modified 3Y-TZP surface. The RGD-immobilized 3Y-TZP can increase the cell adhesion, and thus, improve the biocompatibility of 3Y-TZP.
DP-6 Bioactive Enhancement on the Polyetheretherketone Surface using High Power Impulse Magnetron Sputtered Titanium Dioxide Film
Yi-Ju Yang (Feng Chia University, Taiwan); Hsi-Kai Tsou (Taichung Veterans General Hospital, Taiwan); Ying-Hung Chen (Feng Chia University, Taiwan); Chi-Jen Chung (Central Taiwan University of Science and Technology, Taiwan); Ju-Liang He (Feng Chia University, Taiwan)

Polyetheretherketone (PEEK) resembling human cancellous bone in elastic modulus has been widely applied today as implant material for spinal interbody fusion cages. However, its bio-inertness and hydrophobic surface properties provide poor osseointegration. Titanium dioxide (TiO2) is known to possess excellent osteoblast compatibility due to the negatively charged –OH groups on its surface. This study utilizes a novel technology, high power impulse magnetron sputtering (HIPIMS), beneficial from high ionization rate and ion bombardment energy than the direct current magnetron sputtering (DCMS), to deposit TiO2 coatings with anatase (A-TiO2) and rutile (R-TiO2) phase respectively, onto the PEEK substrate at low temperature. The film adhesion of TiO2 coatings fabricated using HIPIMS and DCMS were compared. The in vitro biocompatibility of these coatings was also confirmed.

The results indicate that utilizing HIPIMS can successfully prepare crystallinic columnar A-TiO2 and R-TiO2 coating on PEEK substrate by controlling the ratio of oxygen to argon without additional substrate heating. The scratch test proved that HIPIMS-TiO2 coatings exhibit cohesive failure indicating a strong adhesive force between the HIPIMS-TiO2 coating and PEEK substrate. Both the capability for inducing hydroxyapatite formation as well as the osteoblast compatibility of HIPIMS-TiO2 coating outperformed than those of the bare PEEK substrate. In addition, the R-TiO2 coating produced better in vitro performance than did the A-TiO2 coating, probably owing to the formation of many –OH groups on its (110) prefer orientated surface. In summary, the HIPIMS-TiO2 met the osseointegration requirements, suggesting the possibility of using HIPIMS to modify the PEEK surface with TiO2 coating for spinal implants.

DP-7 Surface Modification of Blood-contacting Biomaterials by Plasma-polymerized Super-hydrophobic Films using Hexamethyldisiloxane and Tetrafluoromethane as Precursors
Chaio-Ru Hsiao (Feng Chia University, Taiwan); Cheng-Wei Lin (Feng Chia University; Central Taiwan University of Science and Technology, Taiwan); Chia-Man Chou (Taichung Veterans General Hospital; National Yang-Ming University, Taiwan); Chi-Jen Chung (Central Taiwan University of Science and Technology, Taiwan); Ju-Liang He (Feng Chia University, Taiwan)

This work proposes a plasma polymerization system with a pulsed-dc power supply to modify the surface of the widely used biomaterial, polyurethane (PU) using low-cost hexamethyldisiloxane (HMDSO) and tetrafluoromethane (CF4) as precursors. By controlling the HMDSO/CF4 (fH) monomer flow ratio to develop a super-hydrophobic coating, plasma-polymerized HMDSO/CF4 (pp-HC) with micro- and nano-scale coexisted morphology was obtained. Reduction in fibrinogens adsorption and platelets adhesion is expected to improve blood compatibility.

Experimental results reveal that the obtained pp-HC films are with SiOX nanoparticles randomly dispersed on the micrometer scaled three dimensional network film surface. Functional groups -CF, -CF2 bonding and SiOx were detected over the film surface. Water contact angle of the pp-HC coating is ultimately 161.2o, apparently attributed to the synergistic effect of the coexisted micro- and nano-scale surface morphology with a low surface energy layer. It retained super-hydrophobic and anti-fouling characteristics after being rubbed 20 times by using steel wool tester. Results of in vitro cytotoxicity, fibrinogen adsorption and platelet adhesion tests reveal good myoblasts cell proliferation and nearly no fibrinogen adsorption or platelet adhesions on the pp-HC coated specimens. These quantitative findings imply that the pp-HC coating may have the potential to avoid the formation of thrombi and provide an alternative means of modifying the surfaces of blood-contacting biomaterials.

DP-11 Effects of the Sputtering Pressure on the Preparation of Titanium Iodized Films by Reactive Sputtering
Kaori Fujimaki, Yukihiro Sakamoto (Chiba Institute of Technology, Japan)

Iodine is one of essential element for human beings and has bactericidal property and antibacterial action. Also, Titanium and its alloy are used as implant materials because of their biocompatible and safe to the human body. Therefore, titanium iodized is expected to be able to applied in the field of medical technology.

Titanium iodized is the one of compound with titanium and iodine and both elements were bonded in chemically. However, there are only few reports on the preparation of the compound of titanium and iodine using dry process .

On the other hand, particular properties films and non-equilibrium state films can be obtained using dry process methods. Such as compound films can be prepared using reactive sputtering, and the film were formed by chemical reaction with the target material and introduced gas in the vacuum chamber .

The investigation was carried on the effect of the sputtering pressure on the preparation of titanium iodized films by reactive sputtering.

DC reactive sputtering was used to obtain Titanium iodized. Ti (99.7% purity) was used as a target. The experiment condition of reactive sputtering was as follows, sputter gas; mixture of Ar and I2 vapor,substrate; Si, applied power; 50W, pressure; 0.5, 0.8, 1.2 Pa and processing time; 60min, respectively.

The samples were evaluated by Scanning Electron Microscope(SEM),X-ray diffraction (XRD),X-ray Photoelectron Spectroscopy(XPS) ,Electrical Resistivity measurement and tribological property measurement, respectively.

From the observation by SEM, all the samples showed smooth surface. The peak in XRD patterns was broad and it indicated that structure was amorphous. Ti ,I ,O and C peaks were observed in the XPS spectrum. Form the results of XRD and XPS, titanium iodized was could be prepared using reactive sputtering method and its structure was amorphous. Electrical resistivities of the films were showed about 0.03Ω/□. The friction coefficient of the film showed lower than that of the substrate. Especially, the lowest friction coefficient was obtained in the sample prepared at 0.8Pa.

DP-19 Study of the Oxygen Reduction in Low-energy Ion Implantation of Silver Ions in Titanium to Improve Antibacterial Action
Tatiana Soares, Andreia Souza (Universidade de Caxias do Sul, Brazil); Letícia Casarin (Universidade Federal do Rio Grande do Sul, Brazil); Carlos Figueroa (Universidade de Caxias do Sul, Brazil); Eduardo Tondo (Universidade Federal do Rio Grande do Sul, Brazil); César Aguzzoli (Universidade de Caxias do Sul, Brazil)

Biocompatible materials have been widely studied, especially in relation the prevention of surgical and medical intervention resulting from infections due to prosthetics and orthotics infected by microorganisms. Among them, titanium medical class is distinguished by its high degree of biocompatibility. An alternative may be to modify the surface of these materials for implantation of silver ions in a region near to 10 nm in depth, providing them antibacterial properties. However, this process can have its efficiency harmed by the presence of oxygen, which reacts at room temperature with titanium and silver forming a thin oxide layer. This layer can act as a barrier hindering both the process for implantation of ions, and the releasing of Ag+ from inside the metal. The objective of this work is to eliminate the oxide layer, because oxidized silver has no antimicrobial property. Three methods have been proposed in which samples of commercially pure titanium (ASTM F139 and ASTM F67, were washed with acetone in ultrasonic bath and subsequently passed through I) cleaning the surface by plasma etching prior to ion implantation process; II) applying a film of silver after the implantation process; III) perform the cleaning plasma before to implantation, followed by the application of the silver film. In method I, the base pressure of the system was 3.5x10-2 mbar, using a mixture of Ar-H2 gases in proportions of 87% and 13% respectively and a source of direct current (DC) power of 50 W for 30 minutes. In method II, the deposition of the silver film was made immediately after implantation, in the same chamber with pressure 8x10-7 mbar, filament current 16 A for 10 min. The method III consisted of performing pretreatment and following implantation, apply the film, considering the same procedure adopted for each single treatment. The implantation of silver ions (Ag+) in the surface of titanium was by the technique of ion implantation at low energies, 4 keV, in an equipment of Ion Plating Diversified. The dosage of implanted Ag+ was around 6x1015 atoms.cm-2. The RBS spectra confirms that there are no contaminants in samples. For the samples from method I was observed that the profile depth of oxygen presents qualitatively decrease in intensity. The thickness of film applied in method II and III was approximately 3.7 nm. The biological tests are in progress to prove the efficiency of the treatment and the inhibition of biofilm formation and adhesion of pathogenic microorganisms.

DP-21 Anodizing of AZ31 Mg Alloy under Various DC/AC Voltage
Salah Salman (Nagoya University, Japan; Al-Azhar University, Egypt); K. Nishinaka (Art one Co., Ltd, Japan); K. Hikida, K. Kuroda, M. Okido (Nagoya University, Japan)

Magnesium alloys are recognized as alternatives to Al alloys and steel to reduce the weight of structural materials. However, poor corrosion resistance of magnesium alloy hinders the widespread of magnesium alloys in many applications. Therefore, further surface treatment are needed in order to meet industrial requirement specifications. In this research we investigate the anodizing of AZ31 Mg alloy in NaOH alkaline solution using the alternating current, the process was performed by changing the solution temperature, voltage and frequency values. Furthermore, the effect of some additives on the anticorrosion property of magnesium alloy was investigated. The solutions contain 100 mMNa2B4O7 and 10mM KF showed the best corrosion results compared to other additives. At the lower frequency, the film thickness becomes thicker ; leading to good corrosion resistance. The anodic film obtained at AC voltage ±15 V has the best corrosion resistance and the structure of the film was Mg(OH)2/ MgO. The amount of MgO increased with increasing the potential due to the dehydration reaction of Mg(OH)2.

DP-22 Adhesion and Hemocompatibility of Heparin/Collagen Polyelectrolyte Multilayers Coated on Titanium Substrates with a Dopamine Interlayer
Chau-Chang Chou, Hou-Cheng Lin (National Taiwan Ocean University, Taiwan); Chi-Hsiao Yeh (Chang Gung Memorial Hospital at KeelungTaiwan); Rudder Wu (National Institute for Materials Science, Japan); Wen-Jin Cherng (Chang Gung Memorial Hospital at Keelung, Taiwan)

Heparin/collagen multilayers were coated on titanium substrates by using layer-by-layer technology. Dopamine as the interlayer between multilayers and titanium substrates was applied and the coatings’ hemocompatibility and adhesion was investigated. Two different pretreatments on titanium sample were compared. One was submerged into 5M NaOH solution 60℃ for 24 h and another, into 2 mg/ml dopamine solution for 8 h. After finish the pretreatments, two samples were immersed in poly-L-lysine solution for 30 min and then coated with heparin and collagen multilayers by alternatively changing the solutions until the desired number of layers. The surface topography, chemical composition, and hydrophilicity of the films were investigated by scanning electron microscopy, Fourier transform infrared spectroscopy, and water contact angle measurement. The study of the adhesion of the multilayers was conducted by nano-scratch test. The hemocompatibility was evaluated by measuring the hemolysis ratio, platelet covered area and activated-partial-thromboplastin-time (APTT) in vitro. The results indicated that two anticoagulation multilayers was successfully coated on titanium substrates. The use of dopamine as the interlayer between multilayers and titanium substrates is beneficial to enhance the hemocompatibility and adhesion as well.

DP-25 Hybrid Calcium Phosphate Coating with Silicon Doping on Ti-Nb-Zr Alloy by Electro-deposition and Sputtering
Yong-Hoon Jeong (The Ohio State University, USA); HanCheol Choe (Chosun University, Republic of Korea)

Bone is a natural composite that mainly consists of mineral as a calcium phosphate [Hydroxyapatite: Ca10(PO4)6(OH)2, HA] and organic fraction. Bone defect can occur in a variety of clinical aspect, and the synthesis HA-coated metallic implant has been received for hard tissue replacement in recent years. However, usage of HA is limited by its relatively slow rate of biological interaction, and there is also a requirement to improve the success rate of HA-coated implants. Recently, the silicon-doped HA (Si-HA) has been reported that showed the greatest dissolution, suggesting a decrement of grain size can lead to increased solubility and hence greater biocompatibility. As a coating substrate of implant materials, β stabled Ti-Nb-Zr alloy has significant low elastic modulus and has not toxic response than that of pure titanium or Ti-6Al-4V alloy, Ti-35Nb-10Zr alloy has appropriate properties with reasonable mechanical and chemical properties to be used as a coating substrate. The objective of this study was to investigate the hybrid calcium phosphate coating with silicon (Si) doping on biomedical Ti-Nb-Zr alloy.

The Ti-Nb-Zr alloy was manufactured with 35 wt.% of Nb and 10 wt.% of Zr by arc melting furnace and quenched to be a β phase. Electrochemical deposition of calcium phosphate (HA) was performed by pulsing the potential with a method of cyclic voltammetry (30 cyclic times), in the electrolyte with the reagent-grade chemicals of 5 mM·Ca(NO3)2·4H2O + 6.0 mM·NH4H2PO4 at 85 °C. The Si doping process employed a pure Si target and performed by a radio-frequency (RF) magnetron sputtering with variable deposition time and power (30-120 min and 30-100 W) to be Si content of 0.8-2.0 wt.%. The surface characteristics were observed by field-emission scanning electron microscopy, X-ray diffractometer, X-ray fluorescence spectrometer, Fourier transform infrared spectroscopy, and electrochemical corrosion test (potentiodynamic and AC impedance test). These finding indicate that the hybrid Si-doped HA coating layer could be successfully fabricated with chemical (electro-deposition) and physical (sputtering) method, Si-HA layer had higher degradable than that of HA single layer with proving of electrochemical corrosion test. (Supported by NRF: 2013 R1A1A 2006203 &NRF:No.2008-0062283 ;hcchoe@chosun.ac.kr).
DP-27 Morphology of Mg-Doped Hydroxyapatite Coatings on Anodized Ti-xTa Alloys
JeongJae Kim, HanCheol Choe (Chosun University, Republic of Korea)

The CP-Ti and Ti-6Al-4V ELI have been intensively studied for the applications of orthopedic and dental implants because of its excellent mechanical properties, corrosion resistance, and biocompatibility, but it is not strong enough for some dental application. The elastic modulus of human cortical bone is as low as 18 GPa, whereas most metallic implant materials have approximately six- to tenfold higher elastic modulus than cortical bone. Such a large difference in the elastic modulus between a bone and an implant can cause bone resorption induce by stress shielding. Moreover, the Ti-6Al-4V alloy is currently used and should be replaced because the release of Al and V ions causes long-term health problems. Thus, there are efforts for developing new titanium alloys with nontoxic elements. In our research group, it was reported that Ti-30Ta alloys exhibited very low elastic modulus of 60 GPa. To achieve improved osseointegration, there have been many efforts to modify the composition and topography of these implant surfaces.

Hydroxyapatite was widely used as coating ceramic for orthopedic and dental applications given its excellent biocompatibility and strong bonding with natural bones. HAp ceramics can be doped with small amounts of ions that are found in natural bones and tooth mineral. HAp coatings doped with magnesium(Mg) ion is an attractive method to improve the biocompatibility and biodegradability of HAp coatings.

In this paper, we prepared nano-phase HAp film on the anodized binary Ti-xTa alloys (x=10 to 50 wt.%) by electrochemical deposition. The deposition process involved two steps, 1) TiO2 micro-pore formation on Ti-xTa alloys at high current anodization treatment; 2) the electrochemical deposition method was carried out in Mg-ion contained electrolyte for nano-phase HAp deposition on anodized Ti-xTa surface. The electrolyte was a composite solution of Ca(NO3)2·4H2O, NH4H2PO4, and Mg(NO3)2 in deionized water, with (Ca + Mg)/P molar ration being 1.67. Finally, all coatings were gently rinsed in deionized water and dried at the room temperature. Meanwhile, the pure HAp coatings were prepared as the control group. The morphology and crystalline structure of nano-phase Mg/HAp film on the anodized Ti-xTa alloys surface were characterized by thin film XRD and FE-SEM. Elemental analysis was performed using an EDS.

It is expected that Ti-xTa alloys having a high biocompatibility can be obtained by applying the Mg-ion doped nano-phase HAp deposition after the electrochemical anodization(Supported by NRF: 2013 R1A1A 2006203 & NRF: No.2008-0062283; hcchoe@chosun.ac.kr).

DP-28 Nanotubular Structured Oxide Film on the Ti-29Nb-xHf Alloys by Anodization
Seonyeong Park, HanCheol Choe (Chosun University, Republic of Korea)

The Cp-Ti and Ti-6Al-4V alloys were widely used for dental materials due to their mechanical properties and excellent corrosion resistance. However, Cp-Ti was known as bio-inert materials, Ti-6Al-4V alloy has a problem such as high Young modulus, potential loss of the surrounding bone, and to the release of potentially toxic ions from the alloy. To overcome this problem, Ti alloys containing Nb and Hf elements have been used for biomaterials due to low toxicity and high corrosion resistance. Especially, alloying element of Nb was known as β phase stabilizer. The β phase alloy was widely used to replace currently used implant materials. Also, β phase alloy has good biocompatibility and no harmful human body. In order to improve biocompatibility, porous surface on Ti alloys was widely used to orthopedics including bone substitution such as electrochemical method, physical vapor deposition and sand blasting. One of the various ways of surface modification method, nanotubular oxide surface on Ti alloys was expected to improve the bone cell adhesion and proliferation in clinical applications of implants.

In this study, we investigated nanotubular structured oxide film on the Ti-29Nb-xHf alloys by anodization. The Ti-29Nb-xHf alloys contained from 0 wt. % to 15 wt. % Hf contents were manufactured by vacuum arc-melting furnace. The ingots of Ti-29Nb-xHf alloys were homogenized in Ar atmosphere at 1050 ℃ for 1 h followed by quenching into 0 ℃ water. The formation of nanotubular film was conducted by electrochemical method in mixed electrolytes with 1 M H3PO4 + 0.8 wt. % NaF at 30 V for 2 h. Morphology characteristics of Ti-29Nb-xHf alloys were investigated using, optical microscopy (OM), field emission scanning electron microscopy (FE-SEM), X-ray diffractometer (XRD), and energy dispersive X-ray spectroscopy (EDS). Microstructures of Ti-29Nb-xHf alloys were shown needle-like structure to equiaxed structure as Hf content increased. As the Hf content in these alloys increased, the average thickness of the TiO2 nanotubes increased. (Supported by NRF: 2013 R1A1A 2006203 &NRF:No.2008-0062283 ;hcchoe@chosun.ac.kr).

DP-29 The Variation of Nanotube Shape on the Ti-xNb Alloys by Nb Content and Applied Potential
InSeop Byeon, HanCheol Choe (Chosun University, Republic of Korea)

Cp-titanium and Ti-6Al-4V alloys are metallic materials used as a dental implants and orthopedic implants. Titanium (Ti) and its alloys are fast emerging as the most attractive choice for the majority of medical applications. Especially the Ti-6Al-4V alloy has been an important biomaterial in this field for a long period, due to its high specific strength, excellent corrosion resistance and superior biocompatibility. However releases toxic (Al and V) ions into the body, which have the potential of causing undesirable long-term effects such as Alzheimer’s disease and cytotoxic reactions. Recently, new β-type titanium alloys composed of non-toxic and β-stabilizing elements such as Nb have been developed as implant materials.

Among the various methods to improve the interfacial properties and clinical lifetime of Ti-based implants, anodization has attracted great attention due to controllable, reproducible results as well as simple processing. Also, for the improvement of biocompatibility of Ti alloy, we need the two scale surface modification, that is, nano-scale for bioactivity of the implant and micro-scale for osteoblast adhesion.

In this work, Ti-xNb binary alloys contained from 10 wt. % to 50 wt. % contents were manufactured by vacuum arc-melting furnace. The ingots of Ti-xNb alloys were homogenized in Ar atmosphere at 1000 ℃ for 2 h followed by quenching into 0 ℃ water. The formation of nanotubular film was conducted by electrochemical method in mixed electrolytes with 1 M H3PO4 + 0.8 wt. % NaF with various applied potential from 10 V to 40 V. The surface characteristics were investigated using field emission scanning electron microscopy (FE-SEM), x-ray diffract meter (XRD), X-ray fluorescence (XRF) and, energy dispersive X-ray spectroscopy (EDS).

The nanotubes formed on the Ti–xNb alloys surface were transformed from the anatase to rutile structure of titanium oxide. (This research was supported by NRF: 2013 R1A1A 2006203 &NRF:No.2008-0062283 ;hcchoe@chosun.ac.kr).

DP-30 Corrosion Characteristics of Hydroxyapatite Coating Films on Micro-pore Formation on the Ti-35Ta-xNb Alloys
HanCheol Choe, Chae-IkJo Jo, Yeong-Mu Ko (Chosun University, Republic of Korea)

Cp-Ti and Ti-6Al-4V alloy were widely used for dental implant materials due to their light weight, superior biocompatibility and bio-corrosion resistance, good mechanical properties and relatively low elastic modulus. However, Ti-6Al-4V alloy has Alzheimer disease and potential health problem due to Aluminum and Vanadium. For this reason, we investigated new Ti alloy such as Nb, Ta, Zr and Hf. The β-phase Ti alloys were composed of non-toxic and harmless elements. In addition, this alloy can control decreasing the mechanical characteristics such as Young’s modulus. To improve biocompatibility, anodic oxidation was carried out for Ti alloys. Anodic oxidation was known as an easy method for surface treatment and its surface was advantageous for practical applications. Especially, micro-pore structured TiO2 thin film was expected to have high durability because of its high bonding strength. Hydroxyapatite (HA) coating can also be used for facilitate rapid osseo-integration. Hydroxyapatite and Ti alloys have different advantages; they are now considered equally valid anchoring methods with approximately equal success rates.

In this study, we investigated corrosion characteristics of hydroxyapatite coating films on micro-pore formation on the Ti-35Ta-xNb alloys. The alloys were prepared from Ti with 35 wt. % and Nb which contents of 0 to 15 wt. % and were manufactured in arc-melting furnace. The homogenization was performed at 1000 °C for 12 h and then quenched in water at 0°C. Micro-pore formation was carried out using electrochemical method in 0.15 M calcium acetate monohydrate + 0.02 M calcium glycerophospate in 3 min at 25 °C. Electrochemical deposition was carried out using cyclic and voltammetry (CV) method at 85 °C in 5 mM Ca(NO3)2 ∙ 4 H2O + 3 mM NH4H2PO4. Microstructures of the alloys were examined by OM and FE-SEM, and XRD was employed to identify the phases in the Ti-35Ta-xNb alloys. The morphology of the nanotube and HA precipitation was characterized by FE-SEM. (Supported by NRF: No. 2008-0062283, NRF: 2013 R1A1A 2006203; hcchoe@chosun.ac.kr).

. Key word: Ti-35Ta-xNb alloy, Corrosion, Hydroxyapatite, Anodizing, Micro-pore.
DP-33 The Hybrid Graphene Multilayer System (graphene/SiN/graphene) Coupled with Titanium Alloy (Ti6Al4V) - Structural, Mechanical and Corrosion Characterization
Małgorzata Kalisz, Marcin Grobelny, Magdalena Dominik (Motor Transport Institute, Poland)

Titanium and titanium alloys are widely used in a variety of engineering applications, where combination of mechanical and chemical properties is of crucial importance. Aerospace, chemical and automotive industries as well as medical device manufacturers also benefited from the outstanding properties of titanium alloys. Although, titanium alloys exhibit high strength and toughness. However, in some environments (with high fluoride concentration and low pH) they are susceptible to chemical and electrochemical degradation. They may corrode and / or wear, leading to the degradation of material properties. In order to improve the mechanical and electrochemical properties of titanium alloys surface, surface modification is often required

The main objective of this research is to obtain new and innovative materials for titanium alloy (Ti6Al4V) corrosion protection, based on SiN thin film deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) process and its combination with graphene monolayer, obtained by Chemical Vapor Deposition (CVD) process.

The structure, electrochemical corrosion and mechanical behaviour of the alloy systems before and after corrosion process were studied by i.a: Raman spectroscopy, optical microscopy, SEM, potentiostatic measurements and nanohardness tester.

DP-34 Thin Films for Corrosion Protection of Ti6Al4V Titanium Alloy
Marcin Grobelny, Małgorzata Kalisz, Magdalena Szymanska (Motor Transport Institute, Poland)

The physical, chemical and mechanical properties of titanium alloys make this materials an appropriate candidate for a variety of technical applications. The highest strength to weight ratio and an excellent resistance against wet corrosion due to spontaneous formation of a passivating oxide layer have introduced titanium components into the fields of chemical, aerospace, biomedicine engineering and automotive industry. The oxides layers are barrier between the surrounding environment and the underlying metallic titanium. However, in the presence of aggressive anion species, especially fluoride ions F-, oxides layer is not sustainable. Various surface modification technologies have been proposed and investigated with a view to improving the corrosion properties of the surface of titanium alloys. However, the continued search for new methods of surface modification of titanium alloys to improve their corrosion resistance is under way. The paper focuses on the comparative studies of structural, mechanical and corrosion propertiesof Ti6Al4V titanium alloy after surface modification by thin films i.e.: graphene, TiO2, TiN, SiN.

The tests were done by means of voltametric measurements in a fluoride solution. Surfaces of the films and titanium alloy were characterized using atomic force microscope, nanoindentation measurements, scanning electron microscope and Ramman microscopy .

The results presented in this paper have been obtained within the project ”InGrafTi” in the framework of the National Centre for Research and Development, Graf-Tech Programme.

DP-35 Detection of Organophosphates by Increasing Concentrations Using Gold Nano Layers on Silicon Thin Film and Spectral Reflection Measurement in MIR Band
Meir Ochana, David Rotshild (Ariel University, Israel); Tal Havdala (Bar-Ilan University, Israel); Alex Shulzinger (Ariel University, Israel); Amos Sharoni (Bar-Ilan University, Israel); Amir Abramovich (Ariel University, Israel)

Drinking water in the world is exposed to infections arising from bacteria, microorganisms, industrial wastes and pesticides. Current methods for identifying contaminants of this magnitude primarily include chemical methods like HPLC, ELISA and GCMS. These identification methods are based on chemical bonds and chemical reactions with other substances, and are carried out in laboratories causing delays in receipt of results which can take several days. We have developed a new method that can provide real-time response by combining advanced spectroscopy methods and thin metallic layer sensor that considerably enhance sensitivity. Our method utilizes a gold nano-layer on a silicon substrate in order to increase the sensitivity of spectral detection measurements of organophosphates (OP) by increasing the concentrations of the OP at the detection area of the spectroscopic methods. The OP detection and recognition was carried out using Fourier Transform Infra-Red (FTIR) measurement operating in the MIR 400 cm-1 – 4000 cm-1. We demonstrate, using the OP Malathion, that gold coated wafers which were dipped in the OP solution show a much stronger FTIR signal than uncoated wafers. We attribute the increased sensitivity to enhanced adhesion of the OP molecules to the gold. This was further verified by SEM measurements. We are currently developing an improved version of the measurement scheme, fabricating thin film gold-coated ATR crystals that can be measured while in an aqueous solution. This will enable real time detection of micro poisons by FTIR spectral measurements with significantly improved sensitivity, due to the effectively enhanced concentration of the OP on the gold nano-layer concentration on the ATR surface and in.

DP-36 Thin Film Metallic Glass Coated Medical Needles for Property Enhancements
Yusuke Tanatsugu (National Taiwan University of Science and Technology, Taiwan); Chia-Chi Yu (National Taiwan University of Science and Technology (NTUST), Taiwan); Chia-Lin Li, Jinn P. Chu (National Taiwan University of Science and Technology, Taiwan); Sea F. Wang (National Taipei University of Technology, Taiwan)

Syringe needle is one of the most common medical devices that have been widely used. While needle tip designs and injection methods have been developed to achieve painless injection, less attention has been paid to the needle coating, which is also expected to have some influences on the needle performance. Metallic glass (MG) as a prominent class of structural and multifunctional materials exhibits several unique properties such as high strength, high toughness, and good wear resistances mostly due to its amorphous nature. Thus, these MGs are potentially useful for the medical application. In this work, nickel-free Zr-based thin-film MG (or TFMG) coating was deposited on medical needles by magnetron sputtering. Crystalline metallic (Ti) and ceramic (TiN) coatings were coated for comparison. The insertion and retraction forces were measured when needles were inserted into phantom materials, including polyurethane (PU) rubber block and pork muscle with a constant needle speed. TFMG-coated needle showed a significant reduction in both forces of ~66% and ~72%, respectively, which were significantly lower than those of bare needle during testing against the PU rubber. In addition, both forces were slightly increased even after being tested for 10 times, indicating the good durability. Good performances of TFMG are thought to be caused by the relatively low coefficient of friction and hence the non-sticky property is obtained. Thus, TFMG coating appears to be a promising candidate for medical needle which is not only for one time use, but also for repeated uses such as suture needle for sewing skins.

Keywords: syringe needle, thin film metallic glass, coefficient of friction

DP-38 Adverse Testing in Metal-on-metal and CrN-Ag cCoated Hip Replacements
Laurent Espitalier (Wallwork Cambridge Ltd, UK); Danielle De Villiers, Matthew Royle (Queen Mary University of London, UK); Andrew Fox, Sarah Banfield, Jonathan Housden (Wallwork Cambridge Ltd., UK); Amy Kinbrum, Leona Morton, Simon Collins (Corin, UK); Julia Shelton (Queen Mary, University of London, UK)
Adverse testing in hip simulator studies has become increasingly important as standard testing alone does not accurately represent the clinical condition. Adverse conditions observed clinically are believed to have contributed to the failure and subsequent recall of some hip replacements resulting in an increasing interest in testing beyond compliance. Present concern has not only focussed on measuring the wear rate in these tests but also evaluating the ionic release from metallic bearing surfaces and their wear products. Uncoated and CrN-Ag coated heads and cups were tested in a hip simulator under a range of adverse conditions. The results indicate that coating the metallic surfaces successfully decreased both the wear rate and cobalt release in standard and adverse test conditions. Furthermore, the CrN-Ag coating prevented cobalt release even at the relatively high wear rate observed for the lateralised bearing couples.
DP-39 Corrosion Resistance, Nanomechanical and Nanotribological Properties of (TiAlV)Nx Coatings Deposited by Magnetron Sputtering on Biomedical Alloys
Beatriz Alemón, Evaristo Martínez, Martin Flores (Universidad de Guadalajara, Mexico); JoelC. Huegel (Tecnológico de Monterrey, Mexico); Esteban Broitman (Linköping University, IFM, Sweden)

Coatings on metallic biomedical alloys can act both as a barrier to minimize the release of metal ions caused by the presence of a physiological environment and to enhance the wear resistance of the prosthesis materials. Ti6Al4V and CoCrMo alloys are the most common materials used in artificial joints. Both alloys present disadvantages during real use, however, as CoCrMo suffers the release of metal ions while Ti6Al4V exhibits poor wear resistance. To improve the corrosion and wear resistances of both substrate materials, (TiAlV)Nx coatings were deposited on Ti6Al4V and CoCrMo surfaces by magnetron sputtering of Ti6Al4V commercial alloy used as target in an Argon/Nitrogen discharge at a substrate temperature of 350°C. Sets of coated samples were obtained by varying the Ar/N2 gas mixture from 60/40 to 30/70. Field Emission-Scanning Electron Microscopy (FE-SEM) was used to study the film growth morphology and thickness. The nanostructure and depth-profiling chemical composition of the coatings were analyzed by X-Ray Diffraction and X-Ray photoelectron spectroscopy, respectively. The corrosion-resistance experiments were conducted via potentiodynamic polarization test in simulated body fluid at 36.5 ±1.5°C. The nanomechanical properties of the coatings were evaluated by means of nanoindentation test. The nanotribological performance of the films on both substrates were studied via reciprocal friction tests using a 5 µm diamond conical tip at loads of 50 µN and 500 µN. The wear was calculated by measuring the track sizes in a Surface Probe Microscope (SPM). The thickness of the crystalline coatings ranged from 1.57 to 3.31 µm. The potentiodynamic polarization-curves showed lower corrosion current densities for both coated substrates. The nanomechanical tests showed that the hardness (H) of the coating depends on the Ar/N2 mixture proportion. The highest value of H was obtained with 40% of N2 (20.51+/-.72 Gpa) which is 4 times and 3 times higher than the Ti6Al4V and CoCrMo hardnesses, respectively. The (TiAlV)Nx showed a reduction of roughness, friction coefficient and wear rate in comparison to the uncoated substrates. This work suggests that (TiAlV)Nx coatings improve surface properties of these biomedical alloys.

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