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Dissolution kinetics of titanium dioxide nanoparticles: the observation of an unusual kinetic size effect.

Different types of industrially produced titanium dioxide nanoparticles and a precipitated titanium dioxide have been dissolved in aqueous NaCl solutions at temperatures of 25 and 37 degrees C. The titanium concentration in solution with regard to dependence on time has been determined up to 3000 h after starting the dissolution experiment. The effect of particle size, pH value, temperature, background electrolyte concentration, and mass concentration of titanium dioxide exposed to the liquid phase has been studied. The nanoparticles have been characterized by N2 physisorption measurements and XRD. The total dissolved titanium in solution has been determined by adsorptive stripping voltammetry (AdSV) and inductively coupled plasma mass spectrometry (ICP-MS). A new kinetic size effect has been observed. It turns out that this effect can be explained by applying an already existing phenomenological thermodynamic and kinetic model. The model describes all possible phenomena in a colloidal dispersion, nucleation, growth of particles, Ostwald ripening, and dissolution of particles using a uniform concept.

Hydrogen-Ion Concentration↗

Characterisation of bioactive glass coatings on titanium substrates produced using a CO2 laser.

Titanium and its alloys are widely used in load-bearing bioinert implants. Bioactive glasses (BAGs) form a chemical bond with bone, but they are not suitable for load-bearing applications. Creating a BAG coating on a titanium implant could combine the best properties of both materials. The results tend to be poor when conventional firing methods are applied to coat titanium with BAG. A local application of heat to melt the glass can be achieved by a CO2 laser. A new method is introduced to create BAG coatings on titanium locally in a controlled manner, with a focused CO2 laser beam. The coatings produced by this method precipitate calcium phosphate in vitro. Processing parameters (number of coated layers, laser power, and processing atmosphere) providing a firm attachment of the glass and good in vitro bioactivity were identified. XRD analysis showed no crystallisation of the glass due to processing with the laser. EDXA indicated the formation of a calcium phosphate layer, which FTIR suggested to be a hydroxyapatite. The results show CO2 laser processing to be a promising technique for the manufacture of 30-40 microm BAG coatings on titanium.

Air↗

Influence of surface treatments developed for oral implants on the physical and biological properties of titanium. (I) Surface characterization.

We present an investigation of the physico-chemical surface properties of commercially pure titanium coverslips which were submitted to various treatments designed to optimize their topography in view of application in oral implantology. The surface microroughness, chemical composition and water wettability were analyzed on titanium coverslips prepared by mechanical polishing, acid attack in HCl/H2SO4, after mechanical polishing or sandblasting, and titanium plasma-spray. The chemical composition has been measured by Auger electron spectroscopy. The treatments have no major influence on the surface chemical composition and all the samples display a composition approaching that of TiO2 with minor amounts of carbon, sulfur, silicon and calcium as impurities. The roughness has been measured by scanning force microscopy on an area of 20 microns x 20 microns on each sample. Polished titanium is smooth (peak-to-valley roughness 81 nm), whereas the acid-attacked surfaces exhibit a micro-roughness in the microns range (2100 nm for polished and acid attacked; 3600 nm for sandblasted and acid attacked) which is quite reproducible over large areas of the sample. The acid attacked samples present a subsurface layer which contains hydrogen below the native passivating oxide layer. Water wettability measurement shows that all surfaces are hydrophobic with a slightly higher contact angle for the acid attacked surfaces. The different treatments analyzed in this study essentially influence the surface roughness by preserving the chemical composition and the wettability properties of titanium native oxide surface layer.

Dental Polishing↗

Influence of surface treatments developed for oral implants on the physical and biological properties of titanium. (II) Adsorption isotherms and biological activity of immobilized fibronectin.

The influence of titanium surface properties on in vitro adsorption isotherms of fibronectin, promotion of Staphylococcus aureus adhesion, and binding of a monoclonal antibody to the cell-binding domain of fibronectin was examined. Treatments producing different surface roughness were applied to a single side of commercially pure titanium coverslips, which was either mechanically polished (P), or polished and then acid attacked with H2SO4/HCl (PA), or sandblasted and then acid attacked (SLA), whereas the untreated side was blocked by an albumin coating layer. Incubation of the coverslips with concentrations of soluble 3H-labelled fibronectin increasing from 1 to 16 micrograms/ml led to the saturation of all surfaces with immobilized protein from 4 to 16 micrograms/ml. Promotion of S. aureus adhesion by fibronectin adsorbed on all surfaces and binding of the monoclonal antibody to its cell-binding domain was to some extent proportional to the amount of immobilized protein but also showed some minor differences between surfaces. More important material-related differences were observed when fibronectin adsorption isotherms were expressed as a function of the effective, roughness-corrected surface area, yielding amounts of immobilized fibronectin on the rough PA and SLA titanium surfaces which were 50% lower than those adsorbed on either smooth P or polymethylmethacrylate coverslips used as controls. In conclusion, surface treatments increasing the surface roughness of titanium do not increase, but may partly decrease in vitro adsorption of fibronectin. Despite adsorbing different amounts of fibronectin, both rough and smooth titanium surfaces promote normal expression of 2 major functional domains of this protein.

Adsorption↗

An XPS and SEM evaluation of six chemical and physical techniques for cleaning of contaminated titanium implants.

The purpose of the present study was to analyse clinically failed and retrieved implants prior to and after cleaning by means of scanning electron microscopy (SEM) and X-ray induced photoelectron spectroscopy (XPS) as compared to unused controls. Six different chemical and physical techniques for cleaning of contaminated titanium implants were evaluated: 1) rinsing in absolute ethanol for 10 min, 2) cleaning in ultrasonic baths containing trichloroethylene (TRI) and absolute ethanol, 10 min in each solution, 3) abrasive cleaning for 30 s, 4) cleaning in supersaturated citric acid for 30 s, 5) cleaning with continuous CO2-laser in dry conditions at 5 W for 10 s, 6) cleaning with continuous CO2-laser in wet conditions (saline) at 5 W for 10 s. SEM of failed implants showed the presence of contaminants of varying sizes and XPS showed almost no titanium but high carbon signals. XPS of unused titanium implants showed lower levels of titanium as previously reported, probably due to contamination of carbon which increased with time in room air. Cleaning of used implants in citric acid followed by rinsing with deionized water for 5 min followed by cleaning in ultrasonic baths with TRI and absolute ethanol gave the best results with regard to macroscopical appearance and surface composition. However, as compared to the unused implants the results from an element composition point of view were still unsatisfactory. It is concluded that further development and testing of techniques for cleaning of organically contaminated titanium is needed.

Air Abrasion, Dental↗

The early tissue response to titanium and LactoSorb screws.

Fractures of the maxillofacial region are common in the elderly people. Titanium and LactoSorb screws are the widely accepted materials for use in the maxillofacial fractures. This study was undertaken to evaluate the early tissue response following the insertion of both titanium and LactoSorb screws composed of 82% PLLA and 18% PGA in an elderly animal model. In this study, 22 titanium and 22 LactoSorb screws were applied to calvaria of 44 guinea pigs that were 10-11 months old. Animals were sacrificed on postoperative days 3, 7, 14, 30 and 60. Screws were retrieved with surrounding bone tissue and the specimens were prepared for routine histologic examination. All the specimens were evaluated by light microscopy. Histometric analysis revealed that there was no significant difference between LactoSorb and titanium screws for the new bone formation. The biodegradation of LactoSorb screws was not complete by the end of day 60. In conclusion, both materials were well tolerated and induced bone formation without causing adverse tissue response in an elderly animal model. Our results suggest that both LactoSorb and titanium miniplates and screws can be used safely, regardless of the increasing age. However, LactoSorb may be the first choice as it does not require a second operation for removal and has late biodegradation in elderly that keeps its support for a relatively longer time during fracture healing.

Absorbable Implants↗

The effect of long-term deflection on permanent deformation of nickel-titanium archwires.

The clinician must now consider the alloy along with cross-sectional shape and size when selecting archwires. The purpose of this study is to quantify permanent deformation after long-term deflection of available nickel-titanium archwires. Nine nickel-titanium, one beta-titanium and one stainless steel archwires, .016 inch round, were deflected into orthodontic brackets of simulated archform. One lateral incisor was positioned to yield a deflection of 5 mm in a lingual direction. After wire deactivation, deformation was measured at 1, 14, and 28 days. Two-way ANOVA and Tukey's critical difference tests were used to determine statistical differences. The nickel-titanium wires exhibited better springback characteristics and less permanent deformation than the stainless steel and TMA wires. Several wires increased deformation as deflection time increased. No clinically significant difference was found between presently available nickel-titanium wires in terms of permanent deformation, long- or short-term.

Analysis of Variance↗

Relative stiffness of beta titanium archwires.

The number of vendors of beta titanium (TMA type) wires has recently expanded dramatically. Samples of all the available sizes were obtained from most of the major beta titanium vendors. Three new square sizes are now also available. A total of 34 wire samples were tested for stiffness using the new ADA three-point wire-testing jig. Results show that not all beta titanium wires have the same stiffness. The range of variation was from small to large depending on the nominal wire size. There was also a spread of 1.67% to 4.27% in the standard deviation of the average stiffness from vendor to vendor. Burstone's Vari-modulus of elasticity is discussed along with how the properties of beta titanium could be integrated with his concepts. Strategies for using the new sizes of rectangular beta titanium wires for torque are discussed, including their use as working wires and finishing wires. The possibility of replacing stainless steel wires in the final finishing stages is also discussed.

Dental Alloys↗

Marginal adaptation of partial crowns cast in pure titanium and in a gold alloy - an in vivo study.

The aim of the present study was to assess in vivo the marginal integrity of partial crowns cast in pure titanium and in a gold alloy. For this purpose, two groups of 25 molars were prepared for partial crowns and then restored with partial crowns cast in Degulor M gold alloy and in pure titanium. At a subsequent session, replicas were produced using a special impression-taking technique. The scanning electron microscope (SEM) technique was used to perform quantitative margin analysis (Tiffmess 1.8 program). The gold alloy partial crowns displayed significantly (P < 0.05) more continuous margin (marginal quality A, <50 microm), and the titanium partial crowns significantly more marginal quality B (50-100 microm) and C (>100 microm). The results show that better marginal integrity can be achieved with gold alloy than with titanium partial crowns. However, in practical terms the difference in marginal quality is only slight, so that the use of pure titanium for single-tooth restorations is justified.

Cementation↗

High-energy electron and photon therapy to the parotid bed: radiation dose perturbations with a titanium mandibular implant.

Adjuvant radiation therapy to the parotid bed is commonly administered following surgical resection using either a pair of angled wedged photon beams or an ipsilateral mixed-beam portal of electrons and photons. The present study seeks to determine the optimal parotid bed treatment technique in the presence of a titanium mandibular implant by investigating perturbations in the dose distribution deep to this implant for a 15-MeV electron beam and a 6-MV photon beam. A titanium mandibular plate was embedded in a tissue-equivalent phantom, and irradiated with 15-MeV electrons, and 6 MV photons. Radiation doses behind the plate were measured with both thermoluminescent dosimeters and radiographic film. With 15-MeV electrons, there is a clinically significant decrease in the dose beyond the titanium plate, which is most important at 5-mm and 10-mm depths (18-27%). With 6-MV photons the dose at the deep interface of titanium and tissue is reduced by between 15 and 18%, but rapidly drops to < 5% at a depth of 5 mm. In adjuvant treatment to the parotid bed, when the clinical target volume includes tissue positioned deep to a titanium implant, significant underdosage occurs with ipsilateral beam arrangements, especially when electrons are used.

Electrons↗

Microfine zinc oxide is a superior sunscreen ingredient to microfine titanium dioxide.

BACKGROUND: Microfine zinc oxide and microfine titanium dioxide are particulate sunscreen ingredients that absorb broad-spectrum ultraviolet (UV) irradiation. OBJECTIVE: We compare microfine zinc oxide and microfine titanium dioxide for their abilities to attenuate UVA radiation and their relative whiteness in cosmetic formulations. METHODS: UVA attenuation was measured by diffuse reflectance spectroscopy on normal human skin in vivo. Whiteness was determined by reflectance density of dried coatings on a black background of the two particulates at varying concentrations. RESULTS: Microfine zinc oxide demonstrates superior protection compared to microfine titanium dioxide in the UV spectrum between 340 and 380 nm. Microfine zinc oxide is less white than titanium dioxide at all concentrations. CONCLUSION: Microfine zinc oxide is superior to microfine titanium dioxide as a sunscreen ingredient. It is more protective against long-wave UVA and is less white at a given concentration.

Humans↗

Assessment of internal orbital reconstructions for pure blowout fractures: cranial bone grafts versus titanium mesh.

PURPOSE: To assess the adequacy of internal orbital reconstruction in pure blowout fractures using either cranial bone grafts or titanium mesh implants. PATIENTS AND METHODS: The preoperative and postoperative true coronal computed tomography (CT) scans of 58 patients with unilateral pure orbital blowout fractures were included in the study. Demographic data and measurements of the pretreatment size of the defects were tabulated. The accuracy of reconstruction was assessed subjectively by 1 surgeon by scoring the position of the implant/graft, repositioning of orbital soft tissues, and assessment of orbital volume using the uninjured side for comparison. The cross-sectional area of the anterior, middle, and posterior regions of the reconstructed defect was statistically compared with the same locations on the uninjured orbits by scanning the CT scans and calculating the number of pixels within the selected CT slices. A comparison of the accuracy of reconstructions for those reconstructed with cranial bone graft and those with titanium mesh was statistically performed using parametric (for subjective analyses) and nonparametric tests (for cross-sectional area data). RESULTS: Thirty-eight cases were classified as fractures of the orbital floor, 4 as isolated medial wall fractures, and 16 as combined floor/medial wall fractures. There was a statistically significant difference in the surgeon's subjective ratings of adequacy of reconstructions between titanium mesh and bone-grafted groups. Orbits reconstructed with titanium mesh were more accurate than those reconstructed with bone (P <.001). Overall, there was no significant difference in cross-sectional areas between the reconstructed and uninjured orbits in the middle and posterior regions of the defects, but the anterior region showed significantly smaller cross-sectional areas in the reconstructed orbits (P <.001). CONCLUSIONS: Although there was great individual variability and both materials could be successfully used, the orbits reconstructed with titanium mesh showed better overall reconstructions than those reconstructed with bone grafts.

Adolescent↗

Osteolysis in cemented titanium alloy hip prosthesis.

We evaluated 132 consecutively implanted cemented titanium alloy stems (Ti6-Al7-Nb, SLS-88) after a mean follow-up of 6.6 years (range 5-7 years). Almost 30% of the stems showed significant osteolysis, mainly in the proximal stem area. The amount of osteolysis correlated significantly to a typical pain pattern: dull, circular, and occurring at rest. Six stems had already been revised, and another 7 stems were loose clinically and radiologically, which resulted in a Kaplan-Meier survivorship of 95% for stem revisions and 88% for stem failures (revisions plus loose stems). We found that smaller stem sizes tend to increase the development of osteolysis and loosening. Two factors seem to play a role in early loosening of cemented titanium alloy stems: i) increased elasticity of titanium, which leads in small stem sizes to micromotion between the stem and cement and to cement breakage, and ii) corrosion of the cemented titanium alloy stem and subsequent osteolysis in the adjacent bone. The combination of both factors (high elasticity plus corrosion) accelerates the degradation of the bone anchorage of the stem and initiates early loosening. We advise against the further use of cemented SLS-88 titanium alloy stems.

Adult↗

Reconstruction of the ossicular chain with titanium implants.

OBJECTIVES: Since 1994 more than 1300 titanium implants have been used to reconstruct the ossicular chain of the middle ear for chronic otitis media. Two different types of implants were used. First, a total and a partial implant of fixed length, available in numerous different lengths. And second, a total and partial implant that has an adjustable length. The implants are commercially available from 2 different companies. Patients were followed for a postoperative term from 6 to 72 months. METHODS: A wide variety of patients aged 5 to 82 years received a tympanoplasty type III. Those patients whose ossicular chain had been reconstructed with titanium implants since 1994 were evaluated. As implants from one company are fixed in length; implants of a second company are trimmable in length. All prostheses are lightweight and made of pure titanium, fitting most anatomical situations. RESULTS: Earlier results already showed a very low complication rate. Extrusions occurred only in cases of middle ear atalectasis with resorption of interposed cartilage (<1%). No adverse reaction to the prostheses could be seen, even in histologic reviews. An average air-bone gap less than 20 dB(A) for all calculated frequencies of 0.5, 1, 2, and 4 kHz was achieved for 76% of cases; 43% of cases showed a calculated air-bone gap of less than 10 dB(A), only 10% higher than 30 dB(A). CONCLUSION: All implants used offer the proven benefits of titanium, namely high biocompatibility and high stability at a very low complication rate with excellent hearing results for the patients. Titanium implants can highly be recommended to reconstruct the ossicular chain of the middle ear.

Adolescent↗

The effect of short-term temperature changes on superelastic nickel-titanium archwires activated in orthodontic bending.

The bending stiffness of superelastic nickel-titanium archwires is influenced by alterations in mouth temperature. The activation and deactivation phases of a load-deflection loop of superelastic wires have different stress-magnitudes. This investigation compared the effect of short-term cooling or heating on the bending force exerted by nickel-titanium archwires. Two rectangular superelastic and one conventional nickel titanium wire were tested in bending at 37 degrees C. The specimens were tested during the activation phase and during the deactivation phase. The wires were kept at constant strain and the bending force was measured continually while the activated specimens were subjected to cold (10 degrees C) or hot (80 degrees C) water. The test situation simulates a patient's archwire that is subjected to cold or hot drinks or food during a meal. The conventional nickel-titanium wire was marginally affected by brief cooling or heating, regardless of activation phase. In contrast, the superelastic wires were strongly affected by short-term application of cold or hot water. When tested in activation phase, the effect of heating was transient whereas the wires continued to exert sub-baseline bending forces after short-term application of cold water. When tested in deactivation phase, the effect of cooling was transient whereas the wires exerted supra-baseline bending forces after a short-term application of hot water. The effect of short-term temperature changes on the bending stiffness of superelastic nickel titanium archwires is dependent upon the bending phase. Cooling induced transient effects on a wire in its deactivation phase, but prolonged effects when the wire was tested in the activation phase. In contrast, the effect of short-term heating was transient when the wire was tested in the activation phase, but prolonged when the wire was tested in the deactivation phase.

Cold Temperature↗

Comparison of castability and surface roughness of commercially pure titanium and cobalt-chromium denture frameworks.

STATEMENT OF PROBLEM: Titanium is a biocompatible material, but it is not widely used in clinical dentistry for conventional removable denture frameworks. Little research exists on its applicability. PURPOSE: This study compared the casting accuracy and roughness of titanium and cobalt-chromium denture frameworks. MATERIAL AND METHODS: Twenty Kennedy Class II, Division 1 removable partial denture frameworks were fabricated with commercially pure titanium (n = 10) and a cobalt-chromium alloy (n = 10). The casting accuracy of each framework was determined by visual, radiographic, and microscopic methods. The roughness of each polished framework surface was analyzed with atomic force microscopy. RESULTS: The clinical fit, porosities, and microporosities of both types of metal frameworks were qualitatively similar. The surface roughness of polished pure titanium and cobalt-chromium frameworks was 104.43 +/- 69.24 nm and 133.91 +/- 40.92 nm, respectively. This difference was not statistically significant (P >.05). CONCLUSION: The clinical fit, porosity, and surface roughness of the titanium and cobalt-chromium frameworks fabricated for this study were comparable.

Biocompatible Materials↗

Comparative study of circumferential clasp retention force for titanium and cobalt-chromium removable partial dentures.

STATEMENT OF PROBLEM: The interest in using titanium to fabricate removable partial denture (RPD) frameworks has increased, but there are few studies to support its use. PURPOSE: The objective of this study was to compare circumferential RPD clasps made of commercially pure titanium and identical clasps made of 2 different cobalt (Co)-chromium (Cr) alloys by testing insertion/removal and radiographically inspecting the casts for defects. MATERIAL AND METHODS: On refractory casts that represent a partially edentulous mandibular right hemi-arch segment, 36 frameworks were cast from commercially pure titanium (n = 12) and 2 Co-Cr alloys (n = 12 each) with identical prefabricated patterns and the manufacturer-designated investment and casting technique. Each group was divided into 2 subgroups, corresponding to .25-mm and .50-mm undercuts, respectively. No polishing procedures were performed to ensure uniformity. Only nodules and burs were carefully removed with tungsten burs under magnification when necessary. The specimens were radiographed and subjected to an insertion/removal test simulating 5 years of framework use. The data were subjected to analysis of variance and the Tukey complementary test (P<.01) to compare the retentive forces of RPDs made with the different materials. The Student t test (P<.01) was used to compare the retentive forces of RPDs fabricated with the same alloy with different undercuts. RESULTS: A total of 20% of the titanium specimens demonstrated porosity, showing casting difficulties, and any defect detected on the clasps determined the sample replacement. For Co-Cr alloys, casting difficulties were not found. The data were subjected to analysis of variance and the Tukey complementary test to compare materials for the same undercut. For the .25-mm undercut, no significant difference was found between Magnum and Rematitan alloys; they were both different from the Remanium alloy (P<.01). For the.50-mm undercut, no significant difference was found between Co-Cr alloys; they were both different from Rematitan alloy (P<.01). The Student t test used to compare the same alloys with different undercuts showed no significant difference between Remanium with .25-mm and .50-mm undercuts. For Magnum and Rematitan alloys, there was a significant difference between different undercuts (P=.01). CONCLUSION: Within the limitations of this simulation study, the results suggest that commercially pure titanium clasps maintained retention over a simulated 5-year period, with lower retention force than identical Co-Cr clasps.

Analysis of Variance↗

Medical rapid prototyping and 3D CT in the manufacture of custom made cranial titanium plates.

This report describes a new method of custom making cranial titanium plates for the repair of skull defects. We have combined 3D CT imaging and surface modelling with rapid prototyping (RP) technology to produce physical models of our patients' skulls from which custom titanium plates were made. We have expanded the use of image processing tools applied to the CT image data to fabricate a representation of the skull defect. Medical RP models are relatively expensive and particular attention has been paid to developing image processing methods to reduce costs. Our technique used the patient as their own model and generated data from the contralateral side of the head where appropriate. We present the results of 10 patients who have had a custom made cranial titanium plate fitted and discuss the models for these cases. The benefits of our custom made titanium plates are reduced patient attendances to hospital and a more accurate titanium plate which has improved fitting and cosmesis.

Bone Plates↗