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The mechanical behavior ("shape memory") associated with martensitic solid-state transformation in nearly equiatomic Ni-Ti alloy (55-Nitinol) has been studied. Potential dental and medical applications for 55-Nitinol (55% Ni, 1.5% Co, balance Ti, by weight) and for 60-Nitinol (60% Ni, by weight) have been suggested.
Previous studies have shown that the application of a porous Ti-6A1-4V alloy coating results in a substantial decrease in the substrate material fatigue properties. This phenomenon is due to both a microstructural change from the equiaxed alpha-beta microstructure to a lamellar structure and a notch effect created by the porous coating. The lamellar microstructure has been shown to exhibit the worst fatigue properties of the most common structures obtained in Ti-6A1-4V alloy. This study examined various post-sintering heat treatments which would alter the material microstructure and possibly result in improved fatigue performance. The heat treatments examined produced alternate microstructures to the lamellar structure and some approached the totally transformed acicular alpha structure. The acicular alpha structure has been shown to exhibit the best fatigue properties for Ti-6A1-4V alloy in the notched condition.
Particulate wear debris is associated with periprosthetic inflammation and loosening in total joint arthroplasty. We tested the effects of titanium alloy (Ti-alloy) and PMMA particles on monocyte/macrophage expression of the C-C chemokines, monocyte chemoattractant protein-1 (MCP-1), monocyte inflammatory protein-1 alpha (MIP-1alpha), and regulated upon activation normal T expressed and secreted protein (RANTES). Periprosthetic granulomatous tissue was analysed for expression of macrophage chemokines by immunohistochemistry. Chemokine expression in human monocytes/macrophages exposed to Ti-alloy and PMMA particles in vitro was determined by RT-PCR, ELISA and monocyte migration. We observed MCP-1 and MIP-1alpha expression in all tissue samples from failed arthroplasties. Ti-alloy and PMMA particles increased expression of MCP-1 and MIP-1alpha in macrophages in vitro in a dose- and time-dependent manner whereas RANTES was not detected. mRNA signal levels for MCP-1 and MIP-1alpha were also observed in cells after exposure to particles. Monocyte migration was stimulated by culture medium collected from macrophages exposed to Ti-alloy and PMMA particles. Antibodies to MCP-1 and MIP-1alpha inhibited chemotactic activity of the culture medium samples. Release of C-C chemokines by macrophages in response to wear particles may contribute to chronic inflammation at the bone-implant interface in total joint arthroplasty.
The fracture behavior of cast two types of pure Ti and Ti-6Al-4V alloy was understood by acoustic emission (AE) analysis during a fracture toughness test. Specimens for test were cast by the lost wax method using a specially designed Ti casting machine of pressure-different method for dental use. A fatigue crack was inserted from the machined notch tip into the body of a specimen in the range of 0.45-0.55 a/W. Acoustic emission signals released during the fracture toughness test were detected by two sensors attached to both ends of the specimen. Then the signals were recorded and analysed by the PAC 3000/3104 system. From the early stage of the fracture toughness test, AE signals started to be released in all types of specimens tested. A reaction layer with the investment materials of about 50-100 microns was thought to be the result of the AE release from an early stage of the fracture toughness test. A microfracture behavior of the cast pure Ti and Ti alloys was proposed based on the results obtained from the AE releasing pattern and fracture surface findings.
OBJECTIVES: To measure the effect of three special liquid proportions and five forming temperatures on the length of superplastically formed titanium dental implant superstructures made using Rematitan dental casting investment. METHODS: Rematitan dental casting investment was used to make models that contained two implant abutment analogues 8 mm apart. The investment was hand-mixed with 30, 50 or 70% special liquid proportions and ten models of each were made. Dies for superplastic forming (SPF) were made that contained three models (one for each special liquid proportion). Five dies were made for forming at 810 degrees C and five dies for forming at 810, 840, 873, 900 and 927 degrees C using 2 mm thick Ti-6Al-4V discs. The distance between the abutment impressions in the formed discs was measured with a traveling microscope and compared with the distance between the abutments of the master model to determine the most accurately fitting superstructure beam. RESULTS: The proportion of special liquid used to make the SPF models had an unpredictable effect on the length of the superstructure at each forming temperature. Superstructure beams formed at lower temperatures had a better fit compared to the master model for all special liquid proportions. The most accurately sized beams were formed at 810 degrees C. SIGNIFICANCE: SPF can provide an alternative method for the production of dental implant superstructures. The fit was affected predominantly by the forming temperature, but also by the special liquid proportion used for making the SPF investment model.
Biological events occurring at the implant-host interface, including protein adsorption are mainly influenced by surface properties of the implant. Titanium alloys, one of the most widely used implants, has shown good biocompatibility primarily through its surface oxide. In this study, a surface sol-gel process based on the surface reaction of metal alkoxides with a hydroxylated surface was used to prepare ultrathin titanium oxide (TiOx) coatings on silicon wafers. The oxide deposited on the surface was then modified by self-assembled monolayers (SAMs) of silanes with different functional groups. Interesting surface morphology trends and protein adhesion properties of the modified titanium oxide surfaces were observed as studied by non-specific protein binding of serum albumin. The surface properties were investigated systematically using water contact angle, ellipsometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. Results showed that the surface sol-gel process predominantly formed homogeneous, but rough and porous titanium oxide layers. The protein adsorption was dependent primarily on the silane chemistry, packing of the alkyl chains (extent of van der Waals interaction), morphology (porosity and roughness), and wettability of the sol-gel oxide. Comparison was made with a thermally evaporated TiOx-Ti/Si-wafer substrate (control). This method further extends the functionalization of surface sol-gel derived TiOx layers for possible titanium alloy bioimplant surface modification.
A new implant surface has been developed with the purpose of avoiding as much stress shielding as possible, and thus prolong the prosthesis lifespan. The aim of this study was to investigate the in vitro effect of this new ultra-high roughness and dense Titanium (Ti) surface (PG60, Ra = 74 microm) in comparison with medium (TI01, Ra = 18 microm) and high (TI60, Ra = 40 microm) roughness and open porous coatings; all the coatings were obtained by vacuum plasma spraying. MG63 osteoblast-like cells were seeded on the tested materials and polystyrene, as control, for 3 and 7 days. Cells proliferated on the material surfaces similarly to the control. Alkaline phosphatase activity had lower values for TI60 than TI01 (p < 0.0005) and PG60 (p < 0.005). Osteocalcin levels measured on TI60 were significantly (p < 0.0005) lower in comparison with TI01 and PG60 at 7 days. Procollagen-I synthesis reduced with increasing roughness and the lowest data was found for PG60. While at 3 days Transforming Growth Factor beta1 levels augmented with increasing roughness, at 7 days TI60, the high roughness surface, was significantly lower than PG60 (p < 0.005) and TI01 (p < 0.001). All tested materials showed significantly higher Interleukin-6 levels than those of polystyrene at both experimental times. Nitric Oxide activity on TI01 was significantly (p < 0.05) higher than on TI60 and polystyrene. In conclusion, the new ultra-high roughness and dense coating PG60 provided a good biological response, even though, at least in vitro, it behaved similarly to the coatings already used in orthopaedics.
The genotoxicity level of nickel-titanium (NiTi) was compared to that of its pure constituents, pure nickel (Ni) and pure titanium (Ti) powders, and also to 316L stainless steel (316L SS) as clinical reference material. In order to do so, a dynamic in vitro semiphysiological extraction was performed with all metals using agitation and ISO requirements. Peripheral blood lymphocytes were then cultured in the presence of all material extracts, and their comparative genotoxicity levels were assessed using electron microscopy-in situ end-labeling (EM-ISEL) coupled to immunogold staining. Cellular chromatin exposition to pure Ni and 316L SS demonstrated a significantly stronger gold binding than exposition to NiTi, pure Ti, or the untreated control. In parallel, graphite furnace atomic absorption spectrophotometry (AAS) was also performed on all extraction media. The release of Ni atoms took the following decreasing distribution for the different resulting semiphysiological solutions: pure Ni, 316L SS, NiTi, Ti, and controls. Ti elements were detected after elution of pure titanium only. Both pure titanium and nickel-titanium specimens obtained a relative in vitro biocompatibility. Therefore, this quantitative in vitro study provides optimistic results for the eventual use of nickel-titanium alloys as surgical implant materials.
STUDY OBJECTIVE: To study exit-site/tunnel infections and catheter outcomes in peritoneal dialysis patients. DESIGN: The study was designed to investigate exit-site (ESI)/tunnel infections (TI) and catheter losses in all chronic PD catheters inserted in ESRD patients from 9/88 to 9/91. SETTING: Tertiary-referral university hospital. PATIENTS AND METHODS: Seventy-three patients (40 males, 33 females) underwent 78 double-cuff coiled swan-neck catheter implantations surgically. The curettage of exit site was performed weekly for tunnel infection refractory to medical management. The subcutaneous cuff was excised in persistent ESI/TI. RESULTS: Fifty-nine episodes of ESI/TI in 34 patients were observed over 946 patient-months. Thirty-nine patients experienced no ESI/TI, 27 patients had one and seven had two or more episodes of ESI/TI. Four patients had five episodes of peritonitis associated with ESI/TI. Eight recurrent episodes of ESI/TI with S. aureus in 8 patients were treated successfully with Rifampin. Seven subcutaneous cuffs were excised successfully in 7 patients with tunnel infection, five with S. aureus and two with Pseudomonas aeruginosa. No catheter was removed due to ESI/TI or ESI/TI associated peritonitis. CONCLUSIONS: Aggressive exit site care including repeated curettage, excision of the subcutaneous cuff and appropriate antibiotics reduced significantly catheter losses related to ESI/TI.
To study the presence of metals in body fluids and tissues after implantation of metallic biomaterials and possible related diseases, a new approach in Atomic Absorption Spectrophotometry (AAS) was developed. This technique was compared to three traditional methods: mineralisation with acid digestion (method A) also known as "wet method", dry ashing (with or without oxygen) (method B); classic Kjeldaal (method C). The new approach (method D) modifies the mineralisation phase and the instrument operating instructions. Al, Na, Cr, K, Ni, Co, Ti, Fe, Hg, Pb, V, Sb and Cu levels were tested with the four methods on bone, muscle, cartilage, skin, brain, lymph nodes, blood, urine, and hair. Test results were checked by the addition method. Results demonstrated a significantly higher percentage of Al, Cr, Ni, Ti and Hg recovery with the new approach. The advantages of method D are no residue, no redox reaction, insignificant loss of analytes and enhanced sensitivity (at ppb level vs ppm of the other methods). This approach should be considered especially when testing heavy metals and complex matrices. Its disadvantages are that it is more time consuming and requires the presence of an operator.
Electrophoretic deposition (EPD) is a low cost flexible process for producing HA coatings on metal implants. Its main limitation is that it requires heating the coated implant in order to densify the HA. HA typically sinters at a temperature below 1150 degrees C, but metal implants are degraded above 1000 degrees C. Further, the metal induces the decomposition of the HA coating upon sintering. Recent developments have enabled EPD of metathesis-synthesised uncalcined HA which sinters at approximately 1000 degrees C. The effects of temperature on HA-coated Ti, Ti6Al4V, and 316L stainless steel were investigated for dual coatings of metathesis HA sintered at 1000 degrees C. The use of dual HA coatings (coat, sinter, coat, sinter) enabled decomposition to be confined to the "undercoat" (HA layer 1), with the surface coating decomposition free. The tensile strength of the three metals was not significantly affected by the high sintering temperatures (925 degrees C < T < 1000 degrees C). XRD/SEM/EDS analyses of the interfacial zones revealed that 316L had a negligible HA:metal interfacial zone (approximately 1 microm) while HA:Ti and HA:Ti6Al4V had large interfacial zones (>10 microm) comprising a TiO2 oxidation zone and a CaTiO2 reaction zone.
Plasma-sprayed hydroxyapatite (HA) coatings applied to metal substrates can induce a direct chemical bond with bone and hence achieve biological fixation of the implant. However, the poor bonding strength between HA and substrate has been of concern to orthopaedists. In this study, two submicrometre ZrO2 powders stabilized with both 3 and 8 mol% Y2O3 (TZ3Y and TZ8Y, respectively) were incorporated in a plasma-sprayed HA coating on Ti-6Al-4V substrate to investigate the change in phase, microstructure and bonding strength. The results show that ZrO2 composite coatings contain more unmelted particles and greater porosity. During plasma spraying, ZrO2 reacts with the CaO in HA to form CaZrO3 and accelerates HA decomposition to alpha-TCP and Ca4P2O9. Nevertheless, bonding strength increases with increase of ZrO2 content in the range 0 to 10 wt% studied. The higher Y2O3-containing TZ8Y apparently exerts a greater strengthening effect than the lower Y2O3-containing TZ3Y.
Providing a substrate surface with micrometer-sized parallel grooves influences the behavior of cells growing on such substrates in vitro. Cells elongate in the direction of the groove and migrate guided by the grooves. It has been suggested that cellular alignment on microgrooves is predominantly dependent on groove dimensions and that surface chemical variation of the substrate material has little effect. Therefore we seeded primary rat dermal fibroblasts (RDF) on smooth and microgrooved (groove width 1-10 microm, depth 0.5 microm) polystyrene (PS), poly-L-lactic acid (PLA), silicone (SIL), and titanium (Ti) substrates. The production process was found to be more accurate for PS and PLA than for SIL and Ti substrates. A proliferation study, scanning electron microscopy, confocal laser scanning microscopy, and transmission electron microscopy revealed differences between RDF behavior on the materials. Our conclusions are (1) the accuracy of microtexture production by casting depends greatly on the material used; (2) even if no sharp discontinuities are present, microtextures still are potent tools for inducing contact guidance; and (3) besides surface texture, surface chemistry has a definitive influence on cell morphology.
Hydroxyapatite (HA) coatings can be deposited using a hybrid process of plasma electrolysis and electrophoresis, called plasma-assisted electrophoretic deposition (PEPD). HA aqueous suspensions with various pH values were prepared using a modified ultrasonic cleaning bath as an agitator/stirrer. Both DC and unbalanced AC power supplies were used to bias the titanium alloy substrate materials employed in this work. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to observe and analyze coating morphology and microstructure. It was shown that the morphology and composition of the calcium phosphate coatings were significantly influenced by solution pH values; the level of "pure" HA in the coatings' composition corresponded to both solution pH and the type of power supply employed. Loss of hydroxyl radials (i.e., dehydroxylation), which degrades the performance of the hydroxyapatite coating in terms of long-term chemical and mechanical stability, can be virtually eliminated by a combination of high pH and unbalanced AC plasma power. In addition, the underlying TiO2 coatings used to support the HA layer (preproduced by plasma electrolysis process) have a nanoscaled (10-20 nm) polycrystalline structure. TEM studies also revealed a dense, continuous amorphous titania layer (10 nm in thickness) at the interface between the Ti alloy substrate and the TiO2 layer, which may play a role in improving the corrosion resistance of the substrate. Such a nanophase TiO2 layer (if used as a coating alone) may also provide a further improvement in osteoinductive properties, compared to a conventional TiO2 coating on the Ti alloy substrate.
PURPOSE: To report 5 patients with a black material accumulating in the conjunctiva around the titanium peg and sleeve systems. METHODS: Retrospective small case series. The clinical features of 5 patients were reviewed. Histopathologic analysis was performed on specimens from 3 patients. Neutron activation analysis was performed on 1 sample. RESULTS: Five asymptomatic patients with black material accumulating in the conjunctiva at the conjunctival-titanium peg interface were evaluated. All patients had a hydroxyapatite-coated titanium sleeve with a titanium peg in position. Histopathologic analysis performed on specimens from 3 patients revealed a mixed inflammatory cell infiltrate with focal areas of a black, foreign-appearing material showing birefringence under polarized light that was predominantly intracytoplasmic. This black material did not respond to bleaching, and in 2 patients, it showed positive staining for iron (Perls method). The material from one patient was evaluated by neutron activation analysis and was found to contain titanium, aluminum, and vanadium. In 18 to 48 months of follow-up, the presence of the material did not appear to be associated with any problems. CONCLUSIONS: The presence of a black substance accumulating in the conjunctiva around some titanium coupling posts is uncommon and appears to be without any consequence in 18 to 48 months of follow-up. Our analysis revealed this substance to be consistent with titanium alloy (Ti-6Al-4V).
Despite reports associating tissue necrosis with implant failure, the degree to which processes, such as metal toxicity, negatively impact implant performance is unknown. We evaluated representative human peri-implant cells (i.e., osteoblasts, fibroblasts, and lymphocytes) when challenged by Al+3, Co+2, Cr+3, Fe+3, Mo+5, Ni+2, and V+3 chloride solutions (and Na+2 as a control) over a wide range of concentrations (0.01-10.0 mM). Cell responses were measured using proliferation assays, viability assays, and microscopic cell morphology assessments. Differential effects were found to be less a function of the cell type than of the composition and concentration of metal challenge. No preferential immunosuppression was demonstrated. Below 0.01 mM, no metal was toxic. The most toxic metals (i.e., Co, Ni, and V) reduced proliferation (IC50), and viability (LC50) and cell morphology of osteoblasts, fibroblasts, and lymphocytes by <50% at challenge concentrations <1 mM. All other metals tested required >5 mM to exact the same responses. Below 1 mM, these toxic metals also induced alterations in all cell morphology consisting of loss of filopodia or lamellipodia or changes in cell shape. Metals that were toxic at clinically relevant concentrations (less than previously reported values in peri-implant tissues/fluids) include Co (0.6 mM), Ni (0.8 mM), V (0.5 mM) for lymphocytes and Co (0.8 mM), V (0.3 mM), Al (1-5 mM), Fe (1-5 mM) for fibroblasts, and Co (0.8 mM), Ni (0.7 mM), V (0.1 mM) for osteoblasts. Only Co and V were toxic in vitro at concentrations below that detected in vivo in synovial fluid (V at 0.1 mM and Co at 0.8 mM for fibroblasts, and V at 0.4 mM and Co at 0.8 mM on osteoblasts). Thus, soluble Co and V released from Co- and Ti-based alloys, respectively, could be implicated as the most likely to mediate cell toxicity in the periprosthetic milieu.
Titanium alloy has been proposed as a suitable alternative to noble metal alloys in premanufactured metal cylinders for fabricating implant prosthesis frameworks. The interfaces produced by standard lost wax procedures that use titanium and conventional noble metal implant cylinders with both high-fusing (high-palladium) and low-fusing (high-gold) noble metal casting alloys were compared. Elemental analysis by scanning electron microscopy and energy-dispersive spectroscopy (SEM/EDS) of the two titanium cylinders revealed that one commercial product had a composition similar to that for commercially pure titanium and the other had a composition consistent with that for Ti-6Al-4V alloy. The SEM observations and complementary elemental line scans indicated that the interfaces between the titanium cylinders and the two noble metal casting alloys did not meet proposed criteria for acceptable metal-to-metal unions. The interfaces between the noble metal cylinders and noble metal casting alloys did exhibit acceptable unions. The SEM observations and elemental analyses were supported by push-shear test results that showed that the resistance to failure was appreciably greater for interface specimens produced with alloy cast to noble metal cylinders compared with titanium cylinders.
The inflammatory and fibrous responses in a subcutaneous rat model were evaluated around degradable polyurethane urea (PUUR; Artelon), with titanium and tissue culture polystyrene (PS) discs having different surface chemical properties but similar surface topography. Cytokines, viability, cellular response, differentiation of cells and fibrous capsule formation and vascularization was investigated after 1, 7 and 21 days of implantation. The exudates retrieved from the pockets were analysed with respect to the total cell numbers, the proportions of cell types, the differentiation of monocytes/macrophages (ED1, ED2), the DNA content and the viability (LD, Trypan blue). Tumour necrosis factor alpha ((h)TNF-alpha) and interleukin-10 ((h)IL-10) were quantified by ELISA. The number of blood vessels, blood vessel luminal area, blood vessel distribution and the fibrous capsule thickness were analysed. The highest number of cells in the exudates around all implants was detected during the early phase of healing (1-7 days). The proportion of ED2-positive cells in the exudates increased from 2-8% at 1 day to 43-56% at 21 days. The levels of TNF-alpha were low with a decrease at 7 days. After 21 days high amounts of IL-10 in the exudates were detected, in particular around PUUR. This study shows that the transition from inflammation to repair (1-21 days) around PUUR, Ti and PS materials was characterized by a decrease in inflammatory cell influx, an increasing proportion of ED2-expressing macrophages, a biphasic TNF-alpha secretion, an increase of IL-10 and a fibrous capsule formation similar to all materials tested.