Young-Taeg Sul

The electrochemical oxide growth behaviour on titanium in acid and alkaline electrolytes

Titanium implants have a thin oxide surface layer. The properties of this oxide layer may explain the good biocompatibility of titanium implants. Anodic oxidation results in a thickening of the oxide film, with possible improved biocompatability of anodized implants. The aim of the present study was twofold: (1) firstly, to characterize the growth behaviour of galvanostatically prepared anodic oxide films on commercially pure (c.p.) titanium and (2) secondly, to establish a better understanding of the electroche0mical growth behaviour of anodic oxide on commercially pure titanium (ASTM grade 1) after changes of the electrochemical parameters in acetic acid, phosphoric acid, calcium hydroxide, and sodium hydroxide under galvanostatic anodizing mode. The oxide thickness was measured by Ar sputter etching in Auger Electron spectroscopy (AES) and the colours were estimated by an L*a*b* system (lightness, hue and saturation) using a spectrophotometer. In the first part of our study, it was demonstrated that the interference colours were useful to identify the thickness of titanium oxide. It was also found that the anodic forming voltages with slope (dV/dt) in acid electrolytes were higher than in alkaline electrolytes. Each of the used electrolytes demonstrates an intrinsically specific growth constant (nm/V) in the range of 1.4--2.78 nm/V. In the second part of our study we found, as a general trend, that an increase of electrolyte concentration and electrolyte temperature respectively decreases the anodic forming voltage, the anodic forming rate (nm/s) and the current efficiency (nm.cm(2)/C), while an increase of the current density and the surface area ratio of the anode to cathode increase the anodic forming voltage, the anodic forming rate and the current efficiency. The effects of electrolyte concentration, electrolyte temperature, and agitation speed were explained on the basis of the model of the electrical double layer.

The significance of the surface properties of oxidized titanium to the bone response: special emphasis on potential biochemical bonding of oxidized titanium implant

The aim of the present study is to investigate bone tissue reactions to various surface oxide properties, in particular to different surface oxide chemistry of oxidized titanium implants (grade 1). One control and three test screw-shaped implant groups were prepared. Controls were turned implants. Test implants, i.e. S implants, P implants and Ca implants were by the micro-arc oxidation (MAO) method. The surface characterizations were performed with X-ray photoelectron spectroscopy, Auger electron spectroscopy, scanning electron microscopy, X-ray diffractometry and TopScan 3D. Eighty implants were inserted in the femora and tibiae of ten mature New Zealand white rabbits for 6 weeks. The removal torque values (RTQ) showed significant differences between S implants and controls (p=0.022), Ca implants and controls (p=0.0001), Ca implants and P implants (p=0.005) but did not show significant differences between the others (p>0.05). In addition, the bone to metal contact (BMC) around the entire implants demonstrated 186% increase in S implants, 232% increase in P implants and 272% increase in Ca implants when compared to the paired control groups. Based on the comparative analysis of the surface characteristics resulting different bone responses between all groups, it was concluded that surface chemistry and topography separately or together play important roles in the bone response to the oxidized implants.

Qualitative and quantitative observations of bone tissue reactions to anodised implants.

Research projects focusing on biomaterials related factors; the bulk implant material, the macro-design of the implant and the microsurface roughness are routinely being conducted at our laboratories. In this study, we have investigated the bone tissue reactions to turned commercially pure (c.p.) titanium implants with various thicknesses of the oxide films after 6 weeks of insertion in rabbit bone. The control c.p. titanium implants had an oxide thickness of 17-200 nm while the test implants revealed an oxide thickness between 600 and 1000 nm. Routine histological investigations of the tissue reactions around the implants and enzyme histochemical detections of alkaline and acid phosphatase activities demonstrated similar findings around both the control and test implants. In general, the histomorphometrical parameters (bone to implant contact and newly formed bone) revealed significant quantitative differences between the control and test implants. The test implants demonstrated a greater bone response histomorphometrically than control implants and the osteoconductivity was more pronounced around the test implant surfaces. The parameters that differed between the implant surfaces, i.e. the oxide thickness, the pore size distribution, the porosity and the crystallinity of the surface oxides may represent factors that have an influence on the histomorphometrical results indicated by a stronger bone tissue response to the test implant surfaces, with an oxide thickness of more than 600 nm.

Oxidized implants and their influence on the bone response

Surface oxide properties are regarded to be of great importance in establishing successful osseointegration of titanium implants. Despite a large number of theoretical questions on the precise role of oxide properties of titanium implants, current knowledge obtained from in vivo studies is lacking. The present study is designed to address two aspects. The first is to verify whether oxide properties of titanium implants indeed influence the in vivo bone tissue responses. The second, is to investigate what oxide properties underline such bone tissue responses. For these purposes, screw-shaped/turned implants have been prepared by electrochemical oxidation methods, resulting in a wide range of oxide properties in terms of: (i) oxide thickness ranging from 200 to 1000 nm, (ii) the surface morphology of barrier and porous oxide film structures, (iii) micro pore configuration – pore sizes<8 μm by length, about 1.27 μ2 to 2.1 μm2 by area and porosity of about 12.7–24.4%, (iv) the crystal structures of amorphous, anatase and mixtures of anatase and rutile type, (v) the chemical compositions of TiO2 and finally, (vi) surface roughness of 0.96–1.03 μm (Sa). These implant oxide properties were divided into test implant samples of Group II, III, IV and V. Control samples (Group I) were turned commercially pure titanium implants. Quantitative bone tissue responses were evaluated biomechanically by resonance frequency analysis (RFA) and removal torque (RT) test. Quantitative histomorphometric analyses and qualitative enzyme histochemical detection of alkaline (ALP) and acidic phosphatase (ACP) activities were investigated on cut and ground sections after six weeks of implant insertion in rabbit tibia. In essence, from the biomechanical and quantitative histomorphometric measurements we concluded that oxide properties of titanium implants, i.e. the oxide thickness, the microporous structure, and the crystallinity significantly influence the bone tissue response. At this stage, however, it is not clear whether oxide properties influence the bone tissue response separately or synergistically.© 2001 Kluwer Academic Publishers

XPS, AES and SEM analysis of recent dental implants.

Today, surface chemistry modifications of titanium implants have become a development strategy for dental implants. The present study investigated the chemistry and morphology of commercially available dental implants (Nobel biocare TiUnite, Astra AB OsseoSpeed, 3i Osseotite, ITI-SLA). X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy were employed for the analysis of surface chemistry. The morphology was investigated by scanning electron microscopy. The present study demonstrated the major differences of surface properties, mainly dependent on the surface treatment used. The blasting and acid etching technique for the OsseoSpeed, Osseotite and SLA surfaces generally showed mainly TiO(2), but a varying surface morphology. In contrast, the electrochemical oxidation process for TiUnite implants not only produces microporous surface (pore size: 0.5-3.0microm), but also changes surface chemistry due to incorporation of anions of the used electrolyte. As a result, TiUnite implants contain more than 7at.% of P in oxide layer and higher amounts of hydroxides compared to the other implants in XPS analysis. F in OsseoSpeed implants was detected at 0.3% before as well as after sputter cleaning.

The roles of surface chemistry and topography in the strength and rate of osseointegration of titanium implants in bone

The present study investigated the effects of surface chemistry and topography on the strength and rate of osseointegration of titanium implants in bone. Three groups of implants were compared: (1) machine-turned implants (turned implants), (2) machine-turned and aluminum oxide-blasted implants (blasted implants), and (3) implants that were machine-turned, aluminum oxide-blasted, and processed with the micro-arc oxidation method (Mg implants). Three and six weeks after implant insertion in rabbit tibiae, the implant osseointegration strength and rate were evaluated. Surface chemistry revealed characteristic differences of nine at.% Mg for Mg implants and 11 at.% Al for blasted implants. In terms of surface roughness, there was no difference between Mg implants and blasted implants in developed surface ratio (Sdr; p = 0.69) or summit density (Sds; p = 0.96), but Mg implants had a significantly lower arithmetic average height deviation (Sa) value than blasted implants (p = 0.007). At both 3 and 6 weeks, Mg implants demonstrated significantly higher osseointegration strength compared with turned (p = 0.0001, p = 0.0001) and blasted (p = 0.0001, p = 0.035) implants, whereas blasted implants showed significantly higher osseointegration than turned implants at 6 weeks (p = 0.02) but not at 3 weeks (p = 0.199). The present results not only support the hypothesis that biochemical bonding facilitates rapid and strong integration of implants in bone, but also provide evidence for biochemical bonding theory previously proposed by Sul.

Resonance frequency measurements in vivo and related surface properties of magnesium‐incorporated, micropatterned and magnesium‐incorporated TiUnite®, Osseotite®, SLA® and TiOblast® implants

OBJECTIVE To investigate implant stability using resonance frequency measurements of topographically changed and/or surface chemistry-modified implants in rabbit bone. MATERIAL AND METHODS Six groups of microstructured, screw-shaped titanium implants: two oxidized, cation-incorporated experimental implants [Mg implants and MgMp implants with micropatterned thread flanges (80-150 microm wide and 60-70 microm deep)] and four commercially available clinical implants (TiUnite((R)), Osseotite((R)), SLA((R)), and TiOblast((R))) were installed in 10 rabbit tibia for 6 weeks. The surface properties of the implants were characterized in detail using several analytical techniques. Implant stability was measured using a resonance frequency analyzer (Osstell(TM)). RESULTS Surface characterization of the implants revealed microstructured, moderately rough implant surfaces varying 0.7-1.4 mum in S(a) (mean height deviation), but with clear differences in surface chemistry. After 6 weeks, all implants showed statistically significantly higher increases in implant stability. When compared with one another, MgMp implants showed the most significant mean implant stability quotient (ISQ) value relative to the others (P<or=0.016). In terms of increment (DeltaISQ) in implant stability, MgMp implants showed a significantly greater value as compared with Osseotite((R)) (P<or=0.005), TiOblast((R)) (P<or=0.005), TiUnite((R)) (P<or=0.005), SLA((R)) (P<or=0.007), and Mg implants (P<or=0.012). In addition, transducer direction dependence of resonance frequency analysis (RFA) measurements was observed such that the differences in the mean ISQ values between longitudinal and perpendicular measurements were significant at implant placement (P<or=0.004) and after 6 weeks (P<or=0). CONCLUSION The present study found that implant surface properties influence RFA measurements of implant stability. Surface chemistry-modified titanium implants showed higher mean ISQ values than did topographically changed implants. In particular, cation (magnesium)-incorporated micropatterns in MgMp implants may play a primary role in DeltaISQ.

Protein adsorption to surface chemistry and crystal structure modification of titanium surfaces.

ABSTRACT Objectives To observe the early adsorption of extracellular matrix and blood plasma proteins to magnesium-incorporated titanium oxide surfaces, which has shown superior bone response in animal models. Material and Methods Commercially pure titanium discs were blasted with titanium dioxide (TiO2) particles (control), and for the test group, TiO2 blasted discs were further processed with a micro-arc oxidation method (test). Surface morphology was investigated by scanning electron microscopy, surface topography by optic interferometry, characterization by X-ray photoelectron spectroscopy (XPS), and by X-ray diffraction (XRD) analysis. The adsorption of 3 different proteins (fibronectin, albumin, and collagen type I) was investigated by an immunoblotting technique. Results The test surface showed a porous structure, whereas the control surface showed a typical TiO2 blasted structure. XPS data revealed magnesium-incorporation to the anodic oxide film of the surface. There was no difference in surface roughness between the control and test surfaces. For the protein adsorption test, the amount of albumin was significantly higher on the control surface whereas the amount of fibronectin was significantly higher on the test surface. Although there was no significant difference, the test surface had a tendency to adsorb more collagen type I. Conclusions The magnesium-incorporated anodized surface showed significantly higher fibronectin adsorption and lower albumin adsorption than the blasted surface. These results may be one of the reasons for the excellent bone response previously observed in animal studies.

A novel in vivo method for quantifying the interfacial biochemical bond strength of bone implants

Quantifying the in vivo interfacial biochemical bond strength of bone implants is a biological challenge. We have developed a new and novel in vivo method to identify an interfacial biochemical bond in bone implants and to measure its bonding strength. This method, named biochemical bond measurement (BBM), involves a combination of the implant devices to measure true interfacial bond strength and surface property controls, and thus enables the contributions of mechanical interlocking and biochemical bonding to be distinguished from the measured strength values. We applied the BBM method to a rabbit model, and observed great differences in bone integration between the oxygen (control group) and magnesium (test group) plasma immersion ion-implanted titanium implants (0.046 versus 0.086 MPa, n=10, p=0.005). The biochemical bond in the test implants resulted in superior interfacial behaviour of the implants to bone: (i) close contact to approximately 2 μm thin amorphous interfacial tissue, (ii) pronounced mineralization of the interfacial tissue, (iii) rapid bone healing in contact, and (iv) strong integration to bone. The BBM method can be applied to in vivo experimental models not only to validate the presence of a biochemical bond at the bone–implant interface but also to measure the relative quantity of biochemical bond strength. The present study may provide new avenues for better understanding the role of a biochemical bond involved in the integration of bone implants.

The effect of calcium ion concentration on the bone response to oxidized titanium implants

AIM To investigate the effect of calcium concentration on the bone tissue response to Ca-incorporated titanium implants. MATERIALS AND METHODS Two titanium surfaces containing 4.2% and 6.6% calcium were prepared using the micro-arc oxidation process. The implants were inserted in the tibia of nine New Zealand White rabbits. After 6 weeks of healing, the bone response to the implants was quantitatively compared by biomechanical and histomorphometrical measurements. RESULTS Ca 4.2% and Ca 6.6% containing implants revealed no distinctive differences in their qualitative surface chemistry; chemical bonding state of Ca in titanium oxide was mainly calcium titanates. No significant differences were observed between two implants in peak removal torque and shear strength comparisons (P>0.05). Histomorphometrical analyses presented no significant differences in bone-metal contact, bone area and newly formed bone measurements between two implants (P>0.05). CONCLUSIONS From biomechanical and histomorphometrical measurements, the two calcium concentrations in this study did not differ significantly with respect to their influence on the bone tissue response. This similar bone response in rabbit tibiae may be explained by the similarity of the qualitative Ca chemistry in titanium surfaces.