Do ‘passive’ medical titanium surfaces deteriorate in service in the absence of wear?

Globally, more than 1000 tonnes of titanium (Ti) is implanted into patients in the form of biomedical devices on an annual basis. Ti is perceived to be ‘biocompatible’ owing to the presence of a robust passive oxide film (approx. 4 nm thick) at the metal surface. However, surface deterioration can lead to the release of Ti ions, and particles can arise as the result of wear and/or corrosion processes. This surface deterioration can result in peri-implant inflammation, leading to the premature loss of the implanted device or the requirement for surgical revision. Soft tissues surrounding commercially pure cranial anchorage devices (bone-anchored hearing aid) were investigated using synchrotron X-ray micro-fluorescence spectroscopy and X-ray absorption near edge structure. Here, we present the first experimental evidence that minimal load-bearing Ti implants, which are not subjected to macroscopic wear processes, can release Ti debris into the surrounding soft tissue. As such debris has been shown to be pro-inflammatory, we propose that such distributions of Ti are likely to effect to the service life of the device.

Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

Investigation of adsorption of dyes onto modified titanium dioxide

Titanium dioxide (TiO2) nanoparticles with different sizes and crystalloid structures produced by the thermal method and doped with silver iodide (AgI), nitrogen (N), sulphur (S) and carbon (C) were applied as adsorbents. The adsorption of Methyl Violet (MV), Methylene Blue (MB), Methyl Orange (MO) and Orange II on the surface of these particles was studied. The photocatalytic activity of some particles for the destruction of MV and Orange II was evaluated under sunlight and visible light. The equilibrium adsorption data were fitted to the Langmuir, Freundlich, Langmuir-Freundlich and Temkin isotherms. The equilibrium data show that TiO2 particles with larger sizes and doped with AgI, N, S and C have the highest adsorption capacity for the dyes. The kinetic data followed the pseudo-first order and pseudo-second order models, while desorption data fitted the zero order, first order and second order models. The highest adsorption rate constant was observed for the TiO2 with the highest anatase phase percentage. Factors such as anatase crystalloid structure, particle size and doping with AgI affect the photocatalytic activity significantly. Increasing the rutile phase percentage also decreases the tendency to desorption for N-TiO2 and S-TiO2. Adsorption was not found to be important in the photocatalytic decomposition of MV in an investigation with differently sized AgI-TiO2 nanoparticles. Nevertheless C-TiO2 was found to have higher adsorption activity onto Orange II, as the adsorption role of carbon approached synchronicity with the oxidation role.

Ordered mesoporous titanium oxide for thin film microbatteries with enhanced lithium storage

A 3D mesoporous TiO2 material with well-developed mesostructure is prepared in the form of a binder-free thin (100 nm) film and studied as potential candidate for the negative electrode in lithium microbatteries. By appropriate thermal treatments, the selected crystal structure (anatase, rutile, or amorphous), and micro-/mesostructure of the materials was obtained. The effects of voltage window and prelithiation treatment improved first cycle reversibility up to 86% and capacity retention of 90% over 100 cycles. After a prolonged intercalation of lithium ions in ordered mesoporous TiO2 appeared small particles assigned to Li2Ti2O4 with cubic structure as observed from ex-situ TEM micrographs. This study highlights the flexibility of the potential window to which the electrode can operate. Maximum capacity values over 100 cycles of 470 μA h cm−2 μm−1 and 177 μA h cm−2 μm−1 are obtained for voltage ranges of 0.1–2.6 V and 1.0–2.6 V, respectively. The observed values are between 6 and 2 times higher than those obtained for films with 600 nm (80 μA h cm−2 μm−1) and 900 nm (92 μA h cm−2 μm−1) lengths. This indicates that 100 nm thin TiO2 films with high accessibility show finite-length type diffusion which is interesting for this particular application.

Paired Evaluation Of Calvarial Reconstruction With Prototyped Titanium Implants With And Without Ceramic Coating.

To investigate the osseointegration properties of prototyped implants with tridimensionally interconnected pores made of the Ti6Al4V alloy and the influence of a thin calcium phosphate coating. Bilateral critical size calvarial defects were created in thirty Wistar rats and filled with coated and uncoated implants in a randomized fashion. The animals were kept for 15, 45 and 90 days. Implant mechanical integration was evaluated with a push-out test. Bone-implant interface was analyzed using scanning electron microscopy. The maximum force to produce initial displacement of the implants increased during the study period, reaching values around 100N for both types of implants. Intimate contact between bone and implant was present, with progressive bone growth into the pores. No significant differences were seen between coated and uncoated implants. Adequate osseointegration can be achieved in calvarial reconstructions using prototyped Ti6Al4V Implants with the described characteristics of surface and porosity.

Effect Of Particles Of Ashes Produced From Sugarcane Burning On The Respiratory System Of Rats.

The practice of burning sugarcane obtained by non-mechanized harvesting exposes workers and the people of neighboring towns to high concentrations of particulate matter (PM) that is harmful to health, and may trigger a series of cardiorespiratory diseases. The aim of this study was to analyze the chemical composition of the micro-particles coming from sugarcane burning residues and to verify the effects of this micro-particulate matter on lung and tracheal tissues. Micro-particulate matter (PM10) was obtained by dissolving filter paper containing burnt residues in NaCl solution. This material was instilled into the Wistar rats' nostrils. Histological analyses (hematoxylin and eosin - HE) of cardiac, lung and tracheal tissues were performed. Inflammatory mediators were measured in lung tissues by using ELISA. The chemical composition of the particulate material revealed a large quantity of the phthalic acid ester, high concentrations of phenolic compounds, anthracene and polycyclic aromatic hydrocarbons (PAH). Histological analysis showed a reduction in subjacent conjunctive tissue in the trachea, lung inflammation with inflammatory infiltrate formation and reduction of alveolar spaces and a significant increase (p<0.05) in the release of IL-1α, IL-1β, IL-6, and INF-γ in the group treated with PM10 when compared to the control group. We concluded that the burning sugarcane residues release many particles, which have toxic chemical compounds. The micro-particulate matter can induce alterations in the respiratory system.

Chemical And Structural Analyses Of Titanium Plates Retrieved From Patients.

The aim of this study was to evaluate the microscopic structure and chemical composition of titanium bone plates and screws retrieved from patients with a clinical indication and to relate the results to the clinical conditions associated with the removal of these devices. Osteosynthesis plates and screws retrieved from 30 patients between January 2010 and September 2013 were studied by metallographic, gas, and energy dispersive X-ray (EDX) analyses and the medical records of these patients were reviewed. Forty-eight plates and 238 screws were retrieved. The time elapsed between plate and screw insertion and removal ranged between 11 days and 10 years. Metallographic analysis revealed that all the plates were manufactured from commercially pure titanium (CP-Ti). The screw samples analyzed consisted of Ti-6Al-4V alloy, except four samples, which consisted of CP-Ti. Titanium plates studied by EDX analysis presented greater than 99.7% titanium by mass. On gas analysis of Ti-6Al-4V screws, three samples were outside the standard values. One CP-Ti screw sample and one plate sample also presented an oxygen analysis value above the standard. The results indicated that the physical properties and chemical compositions of the plates and screws did not correspond with the need to remove these devices or the time of retention.

Enhanced bone apposition to Brazilian microrough titanium surfaces

It has recently been reported that machined and microrough (micro) Brazilian titanium (Ti) implants have good production standards. The aim of this study was to evaluate in vivo bone formation around 2 different implant surfaces placed in dog's mandible. Thirty-two screw-typed Ti implants were used in this study. Mandibular premolars were extracted in 8 dogs and, after 12 weeks, 2 machined (Neodent Titamax, Brazil) and 2 micro implants (Neodent Titamax Porous, Brazil) were placed in each animal. Biopsies were taken at 3 and 8 weeks post-implantation and stained with Stevenel's blue and Alizarin red for histomorphometric measurements of bone-to-implant contact (BIC), bone area between threads (BABT) and bone area within the mirror area (BAMA). Data were analyzed statistically by two-way ANOVA (α=0.05). While at 3 weeks micro implants exhibited significantly more BIC than machined ones (55 ± 12.5% and 35.6 ± 15%, p<0.05), no significant difference in such parameter was detected at 8 weeks (51.2 ± 21% and 48.6 ± 18.1%, p>0.05). There were no significant differences in BABT and BAMA between the implants. Micro surfaces promoted higher contact osteogenesis. These data indicate that this commercial micro Ti implant surface enhances contact osteogenesis at an early post-implantation period when compared to the machined one.

Effect of phosphate-bonded investments on titanium reaction layer and crown fit

This study analyzed the reaction layer and measured the marginal crown fit of cast titanium applied to different phosphate-bonded investments, prepared under the following conditions (liquid concentration/casting temperature): Rema Exakt (RE) - 100%/237°C, 75%/287°C, Castorit Super C (CS)-100%/70°C, 75%/141°C and Rematitan Plus (RP)- 100%/430°C (special to titanium cast, as the control group). The reaction layer was studied using the Vickers hardness test, and analyzed by two way ANOVA and Tukey's HSD tests (α = 0.05). Digital photographs were taken of the crowns seated on the die, the misfit was measured using an image analysis system and One-way ANOVA, and Tukey's test was applied (α = 0.05). The hardness decreased from the surface (601.17 VHN) to 150 μm (204.03 VHN). The group CS 75%/141°C presented higher hardness than the other groups, revealing higher surface contamination, but there were no differences among the groups at measurements deeper than 150 μm. The castings made with CS - 100%/70°C presented the lowest levels of marginal misfit, followed by RE -100%/237°C. The conventional investments CS (100%) and RE (100%) showed better marginal fit than RP, but the CS (75%) had higher surface contamination.

Effect of laser welding on the titanium composite tensile bond strength

The aim of this study was to analyze the shear bond strength between commercially pure titanium, with and without laser welding, after airbone-particle abrasion (Al2O3) and 2 indirect composites. Sixty-four specimens were cast and divided into 2 groups with and without laser welding. Each group was divided in 4 subgroups, related to Al2O3 grain size: A - 250 µm; B - 180 µm; C- 110 µm; and D - 50 µm. Composite rings were formed around the rods and light polymerized using UniXS unit. Specimens were invested and their shear bond strength at failure was measured with a universal testing machine at a crosshead speed of 2.0 mm/min. Statistical analysis was carried out with ANOVA and Tukey's test (α=0.05). The highest bond strength means were recorded in 250 µm group without laser welding. The lowest shear bond strength means were recorded in 50 µm group with laser welding. Statistically significant differences (p<0.05) were found between all groups. In conclusion, airborne particle abrasion yielded significantly lower bond strength as the Al2O3 particle size decreased. Shear bond strength decreased in the laser welded specimens.

Effect of fluoride-containing solutions on the surface of cast commercially pure titanium

This study evaluated the effects of fluoride-containing solutions on the surface of commercially pure titanium (CP Ti) obtained by casting. CP Ti specimens were fabricated and randomly assigned to 5 groups (n=10): group 1: stored in distilled water at 37 ± 1ºC; group 2: stored in distilled water at 37 ± 1ºC and daily immersed in 0.05% NaF for 3 min; group 3: stored in distilled water at 37 ± 1ºC and daily immersed in 0.2% NaF for 3 min; group 4: stored in distilled water at 37 ± 1ºC; and immersed in 0.05% NaF every 15 days for 3 min; and group 5: stored in distilled water at 37 ± 1ºC and immersed in 0.2% NaF every 15 days for 3 min. Surface roughness was measured with a profilometer immediately after metallographic polishing of the specimens (T0) and at 15-day intervals until completing 60 days of experiment (T15, T30, T45, T60). Data were analyzed statistically by ANOVA and Tukey's test (α=0.05). There was no statistically significant difference (p>0.05) in surface roughness among the solutions. In conclusion, fluoride-containing solutions (pH 7.0) used as mouthwashes do not damage the surface of cast CP Ti and can be used by patients with titanium-based restorations.

Retention force of T-bar clasps for titanium and cobalt-chromium removable partial dentures

The objective of this study was to evaluate the retention force of T-bar clasps made from commercially pure titanium (CP Ti) and cobalt-chromium (Co-Cr) alloy by the insertion/removal test simulating 5 years use. Thirty-six frameworks were cast from CP Ti (n=18) and Co-Cr alloy (n=18) with identical prefabricated patterns on refractory casts from a distal extension mandibular hemi-arch segment. The castings were made on a vacuum-pressure machine, under vacuum and argon atmosphere. Each group was subdivided in three, corresponding to 0.25 mm, 0.50 mm and 0.75 mm undercuts, respectively. No polishing procedures were performed to ensure uniformity. The specimens were subjected to an insertion/removal test and data was analyzed statistically to compare CP Ti and Co-Cr alloy in the same undercut (Student's t-test for independent samples) and each material in different undercuts (one-way ANOVA) (p=0.05). Comparisons between materials revealed significant differences (p=0.017) only for the 0.50-mm undercut. No significant differences (p>0.05) were found when comparing the same material for the undercuts. It may be concluded that for different undercuts, both Co-Cr alloy and CP Ti had no significant differences for T-bar clasps; CP Ti showed the lowest retention force values when compared to Co-Cr alloy in each undercut, but with significant difference only for the 0.50-mm undercut; and both materials maintained the retentive capacity during the simulation test.

Comparative study of chemical and mechanical retentive systems for bonding of indirect composite resin to commercially pure titanium

This study evaluated the effect of chemical and mechanical surface treatments for cast metal alloys on the bond strength of an indirect composite resin (Artglass) to commercially pure titanium (cpTi). Thirty cylindrical metal rods (3 mm diameter x 60 mm long) were cast in grade-1 cpTi and randomly assigned to 6 groups (n=5) according to the received surface treatment: sandblasting; chemical treatment; mechanical treatment - 0.4 mm beads; mechanical treatment - 0.6 mm beads; chemical/mechanical treatment - 0.4 mm; and chemical/mechanical treatment - 0.6 mm beads. Artglass rings (6.0 mm diameter x 2.0 mm thick) were light cured around the cpTi rods, according manufacturer's specifications. The specimens were invested in hard gypsum and their bond strength (in MPa) to the rods was measured at fracture with a universal testing machine at a crosshead speed of 2.0 mm/min and 500 kgf load cell. Data were analyzed statistically by one-way ANOVA and Tukey test (a=5%). The surface treatments differed significantly from each other (p<0.05) regarding the recorded bond strengths. Chemical retention and sandblasting showed statistically similar results to each other (p=0.139) and both had significantly lower bond strengths (p<0.05) than the other treatments. In conclusion, mechanical retention, either associated or not to chemical treatment, provided higher bond strength of the indirect composite resin to cpTi.

Comparative study of two commercially pure titanium casting methods

The interest in using titanium to fabricate removable partial denture (RPD) frameworks has increased, but there are few studies evaluating the effects of casting methods on clasp behavior. OBJECTIVE: This study compared the occurrence of porosities and the retentive force of commercially pure titanium (CP Ti) and cobalt-chromium (Co-Cr) removable partial denture circumferential clasps cast by induction/centrifugation and plasma/vacuum-pressure. MATERIAL AND METHODS: 72 frameworks were cast from CP Ti (n=36) and Co-Cr alloy (n=36; control group). For each material, 18 frameworks were casted by electromagnetic induction and injected by centrifugation, whereas the other 18 were casted by plasma and injected by vacuum-pressure. For each casting method, three subgroups (n=6) were formed: 0.25 mm, 0.50 mm, and 0.75 mm undercuts. The specimens were radiographed and subjected to an insertion/removal test simulating 5 years of framework use. Data were analyzed by ANOVA and Tukey's to compare materials and cast methods (α=0.05). RESULTS: Three of 18 specimens of the induction/centrifugation group and 9 of 18 specimens of plasma/vacuum-pressure cast presented porosities, but only 1 and 7 specimens, respectively, were rejected for simulation test. For Co-Cr alloy, no defects were found. Comparing the casting methods, statistically significant differences (p<0.05) were observed only for the Co-Cr alloy with 0.25 mm and 0.50 mm undercuts. Significant differences were found for the 0.25 mm and 0.75 mm undercuts dependent on the material used. For the 0.50 mm undercut, significant differences were found when the materials were induction casted. CONCLUSION: Although both casting methods produced satisfactory CP Ti RPD frameworks, the occurrence of porosities was greater in the plasma/vacuum-pressure than in the induction/centrifugation method, the latter resulting in higher clasp rigidity, generating higher retention force values.