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The effects of bulk versus particulate titanium and cobalt chrome alloy implanted into the rabbit tibia.

Twenty-eight mature New Zealand white female rabbits were allocated into 4 groups of 7 rabbits. Group 1 received a coiled wire of cobalt chrome alloy (Vitallium) (16 gauge x 1 cm). Group 2 received an equal weight of cobalt chrome particles averaging 15.4 microns in diameter. Group 3 received a coiled wire implant of commercially pure (C.P.) titanium (16 gauge x 1 cm). Group 4 received the same weight of C.P. titanium particles averaging 3.8 microns. The implants were placed through a drill hole in the proximal right tibia; the left tibia served as a prepared but nonimplanted control. The animals were killed after 16 weeks and quantitative histology was performed on undecalcified sections of the implant area. Bulk cobalt chrome and titanium implants were surrounded by a thin, incomplete, fibrous tissue layer with decreased numbers of cells. Trabeculae of bone were present within this connective tissue envelope. Fingerlike projections of bone enveloped the implant where it abutted endosteal bone. Clumped and loosely scattered cobalt chrome and titanium particles were surrounded by a minimal amount of fibrous connective tissue. Smaller particles were present within cells. Hematopoietic cells abutted the bulk or particulate implants directly. There was no evidence of acute or chronic inflammation or foreign body reaction. These results should be contrasted with those of Howie et al. in which intraarticular cobalt chrome particles stimulated a rapid proliferation of macrophages and synovial degeneration after 1 week. This may be due to a direct toxic effect of metals in an intra-articular environment, the smaller particle size used in that study, or to abrasive injury to the hyaline cartilage and subsequent synovitis. Our results underscore the general inert properties of these metals in the short term, when implanted into bone in the sizes and physical forms chosen.

Animals↗

The mechanisms of passive dissolution of titanium in a model physiological environment.

The surface chemistry, oxidation, and disolution kinetics of titanium were measured to establish the mechanisms of passive dissolution in physiological environments. Titanium thin films were immersed in 8.0 mM ethylenediamine-tetraacetic acid in simulated interstitial electrolyte (EDTA/SIE) and maintained at 37 degrees C, 10% O2, 5% CO2 and 7.2 pH for periods of time up to 3200 h (133 days). Two immersion schemes were employed: the integral sequentially determined the titanium released into a solution of accumulated dissolution products; and the differential continuously replenished the test solution. The solutions were analyzed for titanium by electrothermal atomic absorption spectrometry (EAAS), and the sample surfaces were analyzed by Auger electron spectroscopy (AES) and x-ray photoelectron spectroscopy (XPS) to determine oxide composition, stoichiometry, and thickness. Prior to immersion two types of hydroxyl (OH) groups were distinguished on the TiO2 surface. Upon immersion, the chemistry of the surface changed as a function of immersion: the presence of OH groups increased and P (nonelemental) was detected at the surface. The dissolution kinetics obeyed a two-phase logarithmic model, where the transition between phases occurred simultaneously with the adsorption of the P-containing species. The dissolution kinetics depended on surface reactions, electric field strength, and molecular diffusion. These mechanisms explain the observed dependence of dissolution kinetics on the properties of the surface oxide and solution ligands.

Edetic Acid↗

Storage and elimination of titanium, aluminum, and vanadium salts, in vivo.

Hamsters were injected with titanium, aluminum, and vanadium salts either intraperitoneally or intramuscularly to study the transport, storage, and elimination of these metals. Blood samples were taken at 4 h or 24 h, and urine samples were taken at 24, 48, and 72 h. The hamsters were then injected weekly for 5 weeks after the initial injection. Blood and portions of the kidneys, liver, lung, and spleen were taken at sacrifice. All samples were analyzed for titanium, aluminum, and vanadium concentrations using graphite furnace atomic absorption spectroscopy (GFAAS). Titanium was found not to be excreted in the urine, was found in low levels in the blood, and was elevated over control in the kidney, liver, and spleen. Aluminum detection via GFAAS showed wide standard deviations and high levels in controls; however, aluminum was found to be excreted in the urine, and to be transported by the blood in the experimental animals. A small amount accumulated in the liver and spleen. Vanadium was excreted in high levels in the urine. A small amount was found in the blood, and the level in the organs was below the reliable detection limits. The rapid excretion of vanadium might be related to its solubility in physiological conditions, while the limited excretion of titanium may be related to its being insoluble in the physiologic environment.

Aluminum↗

Bonding of low-fusing dental porcelain to commercially pure titanium.

The objective of the investigation was to study the basic problems related to the firing of dental porcelain to commercially pure titanium. The firing of a low-fusing porcelain to sandblasted or electrolytically polished titanium was carried out in an ordinary dental furnace. The interfacial regions between the ceramic coatings and titanium were analyzed using scanning acoustic microscopy (C-SAM) and scanning electron microscopy (SEM) techniques. Thermal stresses in the joints were evaluated by means of a finite element model based on multilayer elastic strain analysis. The chemical reactions and their formation sequence at 750 degrees C was predicted thermodynamically and observed experimentally both at 750 and 800 degrees C. The C-SAM results gave evidence that the integrity of the porcelain-titanium joints are better in the sandblasted samples than in the electropolished ones, where defects were larger. SEM analyses of the same samples confirmed the C-SAM findings. Because the reaction layers are more continuous in the electropolished samples, cracks propagated more readily in these samples during the cooling procedure. Both thermodynamic calculations and experimental chemical analyses strongly indicate that the cause for the cracking of the reaction zone is thin layer of Ti (oxo)silicide and/or a relatively thick solid solution layer of Ti and oxygen.

Dental Bonding↗

Mechanical properties of the binary titanium-zirconium alloys and their potential for biomedical materials.

Mechanical properties of titanium-zirconium binary alloys were investigated in order to reveal their possible use for new biomedical materials and to collect useful data for alloy design through a hardness test, a tensile test, and optical microscopy. The hardness of the alloy containing 50% zirconium was approximately 2.5 times as large as the hardness of pure titanium and pure zirconium. Tensile tests showed a similar tendency. No changes between hardness of as cast specimens and as homogenized specimens were observed, nor were changes in microstructures noted. Comparisons between the Ti-6Al-4V alloy and the Ti-Zr-6Al-4V alloy indicated that a titanium-zirconium alloy could provide a base material for a new biomedical alloy. From these results, it was concluded that new alloys for biomedical materials should be designed as titanium-zirconium base alloys.

Alloys↗

Characterization of thin hydroxyapatite layers formed on anodic titanium oxide films containing Ca and P by hydrothermal treatment.

An anodic titanium oxide film containing Ca and P (AOFCP) was formed on commercially pure titanium which was anodized in an electrolytic solution of dissolved beta-glycerophosphate (beta-GP) and calcium acetate (CA). Hydroxyapatite (HA) crystals were precipitated by hydrothermally heating the AOFCP at 300 degrees C. After hydrothermal treatment, the film was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray microanalysis (EDX), and tensile tests. The morphology, composition, and amount of HA crystals precipitated were significantly affected by the composition of the electrolytes. Near-stoichiometric HA crystals with high crystallinity were precipitated completely covering the AOFCP surface at specific electrolyte concentrations. The HA layers were thin at 1-2 microns in thickness. The adhesive strength of the film increased with decreasing electrolyte concentration and the maximum value was about 40 MPa. In vitro tests for 300 days suggested that the stability of the film was high. The high adhesive strength may result from the AOFCP existing as an intermediate layer between the HA layer and a titanium substrate. The intervention of the AOFCP may have prevented abrupt changes in Ca and P content at an HA coating-titanium interface as seen in a plasma-sprayed one. The porous TiO2 matrix of the AOFCP may be suitable for nucleation sites of HA crystals, as well as SiO2 matrix of silicate bioactive glasses or glass ceramics.

Acetates↗

Thromboresistance of alkali- and heat-treated titanium metal formed with apatite.

Fibrin deposition and platelet adhesion onto alkali- and heat-treated titanium metal (AH-Ti), alkali- and water-treated titanium metal (Wa-Ti), and alkali- and heat-treated titanium metal formed with apatite (Ap-Ti) in simulated body fluid (SBF) were evaluated by exposure to anticoagulated blood or washed platelet suspension (WPS) under static conditions and subsequent observation with scanning electron microscopy (SEM). The results were compared with those for commercially pure titanium metal (cp-Ti). Thrombus formation on AH-Ti and Wa-Ti, which were exposed to heparinized whole blood for 1 h, was significantly less than that on cp-Ti, on which pronounced depositions of fibrin-erythrocytes and lymphocytes were observed. No thrombus was observed on Ap-Ti, possibly because of a high adsorption of heparin. Morphological change of platelets attached to surfaces via adsorbed plasma proteins was found to a significant extent on AH-Ti and Wa-Ti exposed to WPS. However, there was almost no difference between cp-Ti and Ap-Ti in round morphology of adherent platelets. These findings suggested that Ap-Ti exhibits stronger antithrombogenic characteristics than cp-Ti and other materials examined in heparinized blood.

Adsorption↗

Biology of alkali- and heat-treated titanium implants.

In cementless fixation systems, surface character is an important factor. Alkali and heat treatments of titanium metal have been shown to produce strong bonding to bone and a higher ongrowth rate. In this study we examined the effect of alkali and heat treatments on titanium rods in an intramedullary rabbit femur model, in regard to the cementless hip stem. The implant rods were 5 mm in diameter and 25 mm in length. Half of the implants were immersed in 5 mol/L sodium hydroxide solution and heated at 600 degrees C for 1 h (AH implants), and the other half were untreated (CL implants). The rods were implanted into the distal femur of the rabbits; AH implants into the left femur and CL implants into the right. The bone-implant interfaces were evaluated at 3, 6, and 12 weeks after implantation. Pull-out tests showed that the AH implants had a significantly higher bonding strength to bone than the CL implants at each time point. As postoperative time elapsed, histological examination revealed that new bone formed on the surface of both types of implants, but significantly more bone made direct contact with the surface of the AH implants. At 12 weeks, approximately 56% of the whole surface of the AH implants was covered with the bone. In conclusion, alkali- and heat-treated titanium offers strong bone bonding and a high affinity to bone as opposed to a conventional mechanical interlocking mechanism. Alkali and heat treatments of titanium may be suitable surface treatments for cementless joint replacement implants.

Animals↗

Effect of alkaline treatment of pure titanium and its alloys on the bonding strength of dental veneering resins.

Commercially pure titanium (cpTi), Ti6Al4V, an experimental beta-type titanium (Ti 53.4 wt%, Nb 29 wt %, Ta 13 wt %, and Zr 4.6 wt %), and 12% AuPdAg alloy plates were sandblasted, cleaned in water, and dried. cpTi plates were treated with nine alkaline treatments that differed in the type of alkali, alkaline concentration, soaking temperature, soaking time, and heating temperature. cpTi plates that were only sandblasted or sandblasted and oxidized at 600 degrees C for 1 h in air were also prepared. Finally, the bonding strengths of 11 kinds of surface-treated cpTi to resin were measured using a pull-shear bonding method after immersion in physiologic saline solution at 37 degrees C for 24 h. The bonds of the standard alkaline-treated cpTi and two titanium alloys to resins were 1.5-1.9 times stronger than those of sandblasted specimens (p < 0.01), but no significant effects of the alkaline treatment were observed on the 12% AuPdAg alloy. The greatest bonding strengths were found for cpTi treated with NaOH and KOH and then heated at 600 degrees C (p < 0.01). In conclusion, alkaline treatment is a simple, effective surface modification of titanium that improves bonding to veneering resin.

Alloys↗

Fracture associated with hydrogen absorption of sustained tensile-loaded titanium in acid and neutral fluoride solutions.

The fracture of commercial pure titanium in acid and neutral fluoride solutions has been examined by a sustained tensile-loading test and hydrogen thermal desorption analysis. It was found that the fracture of titanium occurred in neutral 2.0% NaF solution as well as in 2.0% acidulated phosphate fluoride (APF) solution. The time to fracture decreased with increasing applied stress in both 2.0% APF and 2.0% NaF solutions. In the case of the same applied stress, the time to fracture in the 2.0% APF solution was shorter than that in the 2.0% NaF solution. General corrosion was exhibited on the side surface of the tested specimens. The formation of sodium titanium fluoride was observed on the surface of the immersed specimens in the 2.0% APF solution. Hydrogen desorption of the tested specimen in the 2.0% APF solution was observed with a peak at approximately 600 degrees C. The amount of absorbed hydrogen was >300 mass ppm in the 2.0% APF solution under an applied stress for 24 h. The results of the present study imply that applying stress to titanium by immersing in fluoride solutions leads to the degradation of its mechanical properties.

Biocompatible Materials↗

Effects of interleukin-10 on titanium particle-induced macrophage transcription factor activation and cytokine expression in vitro.

This study tests the hypothesis that transcription factor activation by exposure of macrophages to titanium particles can be modulated by the addition of the antiinflammatory cytokine, interleukin 10 (IL-10). The experiments were carried out with primary human monocyte/macrophages that were treated in the presence or absence of IL-10 with and without exposure to titanium particles. The time course for experiments varied from 1 h-5 h for analysis of nuclear protein and up to 48 h for analysis of cytokine release. Transcription factor translocation to the nucleus was analyzed using electrophoretic gel shift assays and cytokine release was quantified by enzyme-linked immunosorbent assay. Addition of titanium particles increased release of tumor necrosis factor-alpha (TNF-alpha), interleukin-6 (IL-6), and interleukin-1 beta (IL-1 beta). In addition, titantium particle induced translocation of the transcription factors, NF-kappa B and NF-IL6, in the nucleus within 1 h. Treatment of macrophages with IL-10 prior to exposure to titanium particles decreased translocation of NF-IL6 but did not significantly alter nuclear levels of NF-kappa B. In addition, pretreatment of the cells with IL-10 decreased particle-induced cytokine release. These data show that antiinflammatory cytokines may provide a mechanism by which particle-induced inflammatory response may be modulated in vivo.

CCAAT-Enhancer-Binding Protein-beta↗

Effect of titanium dioxide on the oxidative metabolism of alveolar macrophages: an experimental study in rats.

Metallic implants of titanium are used therapeutically in biomedicine because of its excellent biocompatibility. However, no metal or alloy is completely inert. We have previously shown that titanium oxide (TiO(2)) is transported in blood by phagocytic monocytes and deposited in organs such as liver, spleen, and lung 6 months after intraperitoneal injection (ip). Furthermore, it is well known that exposure to metal traces alters the cellular redox status. Thus, the aim of the present study was to determine the presence of titanium in target organs after chronic exposure, assess the potential structural alterations, and evaluate the oxidative metabolism of alveolar macrophages (AM) in the lung. Rats were ip injected with 1.60 g/100 g body wt of TiO(2) in saline solution. Organs (liver, spleen, lung) were processed for histological evaluation. Reactive oxygen species (ROS) in AM obtained by bronchoalveolar lavage (BAL) were evaluated using the nitroblue tetrazolium test and quantitative evaluation by digital image analysis. The histological analysis of organs revealed the presence of titanium in the parenchyma of these organs with no associated tissue damage. Although in lung alveolar macrophages TiO(2) induced a significant rise in ROS generation, it failed to cause tissue alteration. This finding may be attributed to an adaptive response.

Animals↗

Assessment of the cytocompatibility of different coated titanium surfaces to fibroblasts and osteoblasts.

Over the years, many metal and polymer implants have been developed for internal fracture fixation. However, there are always some problems associated with their application, such as implant loosening or infection. This study describes how the morphology and adhesion of both fibroblasts and osteoblasts to two manufactured commercially pure, medical implant-quality anodized titanium surfaces (TS and TSS), and five modified titanium surfaces (TLF, low friction gray anodized titanium; TIG, nitrogen ion implanted TSS; THY, TSS grafted with sodium hyaluronate; TAST, TSS coated with hydrophilic hydrogel; and TT, tiodized TS) were used to obtain an indication of their relative cytocompatibility and to assess which modified surface could potentially be used in vivo. Small variations were observed both qualitatively and quantitatively in the spreading and adhesion of fibroblasts and osteoblasts to the studied surfaces. Overall, fibroblast spreading and adhesion were greatest on the TIG and TLF surfaces. Osteoblast spreading and adhesion were greatest on TS, TIG, and TAST surfaces. No fibroblasts or osteoblasts were found attached to the THY-coated surfaces. Coating medical implant-quality anodized titanium surfaces (TS and TSS) with a TLF, TAST, or more specifically TIG could probably improve soft tissue adhesion and/or osseointegration of bone in vivo. However, it seemed that a hyaluronic acid coating (THY) has potential as a coating in areas where cell adhesion is undesirable, such as orbital fractures, where muscles should avoid adhesion to the implant, and distal radius fractures, where tendons should freely glide over the implant.

Animals↗

Thin calcium phosphate coatings on titanium by electrochemical deposition in modified simulated body fluid.

Adherent and optically semitransparent thin calcium phosphate (CaP) films were electrochemically deposited on titanium substrates in a modified simulated body fluid at 37 degrees C. Coatings deposited by using periodic pulsed potentials showed better adhesion and better mechanical properties than coatings deposited with use of a constant potential. Scanning electron microscopy was used to study the morphology of the coatings. The coatings displayed a polydispersed porous structure with pores in the range of a few nanometers to 1 mum. Furthermore, X-ray diffractometry and the O(1s) satellite peaks in X-ray photoelectron spectroscopy indicated that the coatings possessed a similar surface chemistry to that of natural bone minerals. These results were confirmed by inductively coupled plasma optical emission spectrometry, which yielded a Ca:P ratio of 1.65, close to that of hydroxyapatite. Contact mode atomic force microscopy (AFM) showed the average thickness of the coatings was in the order of 200 nm. Root-mean-square (RMS) roughness values, also derived by AFM, were shown to be much higher on the titanium-CaP surfaces in comparison with untreated titanium substrates, with RMS values of about 300 and 110 nm, respectively. Cell culture experiments showed that the CaP surfaces are nontoxic to MG63 osteoblastic cells in vitro and were able to support cell growth for up to 4 days, outperforming the untreated titanium surface in a direct comparison. These easily prepared coatings show promise for hard-tissue biomaterials.

Adhesiveness↗

Effect of an acidulated fluoride etchant on bonding between titanium and two luting materials.

Adhesive bonding between resin and titanium is useful for resin-bonded prostheses. The purpose of this study was to investigate the efficacy of an etchant, consisting of ammonium hydrogen fluoride (AHF) and phosphoric acid (PA), in titanium bonding. Cast specimens of commercially pure titanium were air-abraded with alumina and etched for 30 s, after which a primer (ALP) was applied. An acrylic rod was bonded to the specimen with one of the two luting agents being examined (Super-Bond QUICK and Panavia F2.0). Shear bond strengths were determined following 10,000 thermocycles. When Panavia F2.0 was applied, neither the etchant nor the ALP primer showed significant effect on bond strength. The postthermocycling bond strength of Super-Bond QUICK was significantly improved with the use of an etchant and ALP primer. Although microscopic observation revealed that considerable numbers of submicron pits were created on the specimens etched using AHF with PA, no significant difference in bond strength was detected in the application of AHF, with or without PA. The present findings suggested that the improved bonding durability was due to the micromechanical retention between the resin and the microscopically roughened titanium surface.

Boron Compounds↗

Preliminary beta-tricalcium phosphate coating prepared by discharging in a modified body fluid enhances collagen immobilization onto titanium.

Because of its excellent scaffold properties toward bone cells, collagen has been recognized as a promising extracellular matrix protein for surface modification of titanium implants. Hydroxyapatite (HA) coatings have been investigated as a preliminary coating for collagen immobilization on titanium implants. However, the composition of HA-collagen is recognized as being difficult, and while many studies have suggested that biodegradable beta-tricalcium phosphate (beta-TCP) has better osteoconductivity than HA, the efficiency of preliminary beta-TCP coating for collagen immobilization on titanium surfaces has yet to be evaluated. This investigation aimed to evaluate the applicability of HA and beta-TCP coatings, prepared by discharging in modified body fluids, as preliminary collagen coatings. To increase collagen induction on preliminary HA and beta-TCP coatings, we used a new cathodic polarization method. X-ray photoelectron spectroscopy revealed that the bonding strength between the collagen NH(+) amino groups of collagen and phosphate (PO(4) (3-)) was greater on the beta-TCP coating than the HA coating. The preliminary beta-TCP coating was tightly crosslinked with RCOO(-) carboxyl groups of the collagen molecules and showed high cellular responses, even in the early stage of cell cultivation. Thus, this coating was found to be more effective than HA as a preliminary coating for collagen immobilization on titanium implants.

Animals↗

Fracture of titanium plates used for mandibular reconstruction following ablative tumor surgery.

PURPOSE: The purpose of this study was to identify reasons for fracture of titanium mandibular reconstruction plates, when used to bridge lateral mandibular defects after ablative tumor surgery. MATERIALS AND METHODS: Sixteen titanium reconstruction plates from sheep mandibles were examined to identify reasons for the plate fractures. The broken plates and the seemingly unbroken plates were examined separately. The plates were removed from the mandibular bone and inspected by dye penetrant examination, metallography, optical microscope, scanning electron microscope, and energy dispersive X-ray spectrometer. Furthermore, axial load fatigue tests were performed in two different environments, air and physiologic salt solution, 0.9% NaCl, to compare titanium behavior in air and the human body. RESULTS: The site of crack initiation was the inner curvature of the reconstruction plate, and the cracks initiated as a result of stress concentration in the shoulder fillet of the plate. The cracks grew in a cyclic manner under masticatory loading of the mandible and the plate. The plate fracture occurred by means of fatigue. The corrosive environment did not affect the failure of the titanium plate, and the fracture was not caused by hydrogen embrittlement. The results revealed that the fatigue properties of the plates may have been impaired by the residual stresses generated in plate bending. CONCLUSIONS: Adjustive bending of the plates, in the surgical operation, may thus be an important cause of fracture of the reconstruction plates, because of generated residual stresses, which affect the mean stress in fatigue loading. To make the plates function without failure the plates should match closely with the three-dimensional shape of the mandible, to avoid any bending in the operative phase.

Animals↗

Evaluation of the titanium dioxide approach for MS analysis of phosphopeptides.

The affinity of titanium dioxide for phosphate groups has been successfully used for enrichment of phosphopeptides from complex mixtures. This paper reports the relationship between the occurrence of some amino acids and the phospho-specific and nonspecific binding of peptides that occurs during titanium dioxide enrichment. In order to perform a systematic study, two well-characterized peptide mixtures consisting of either 33 or 8 synthetic phosphopeptides and their nonphosphorylated analogs, which differed in charge and hydrophobicity, were synthesized and analyzed by ESI-MS and MALDI-MS. The titanium dioxide procedure was also evaluated for comprehensive detection of phosphopeptides in phosphoproteomics. In summary, our results clearly confirm the high selectivity of titanium dioxide for phosphorylated sequences. Drastically reduced recovery was observed for phosphopeptides with multiple basic amino acids. Nonspecific binding of nonphosphorylated peptides and sample loss of phosphopeptides must also be taken into account.

Animals↗