Comparative in vitro performances of bare Nitinol surfaces.

Comparative fibrinogen adsorption and platelet morphology were evaluated on a wide array of well-characterized Nitinol surfaces (polished, chemically etched, boiled in water, electropolished in different electrolytes and heat treated). XPS, SEM, AFM, atomic adsorption spectroscopy and electrochemistry were employed to acquire information on surface chemistry, topography and Ni release. Obtained surfaces, of various topographies and crystallinity from mostly amorphous to nano-crystalline with Ni concentration from 1 to 8%, induced Ni release into biological medium in a subtoxic range (0-11 ng/ml/cm(2)). Fibrinogen adsorption to Nitinol surfaces ranged from that characteristic to pure Ni (130 ng/cm(2)) to pure Ti (300 ng/cm(2)). It was directly proportional to the Ti surface concentration and correlated with open circuit potential related to surface charge. Human platelet morphology varied from round to fully spread depending on surface treatment. Base layer of fully spread cells detected on all surfaces could be even and smooth with no propensity for thrombosis or sticky causing platelet aggregation and thrombus-like structures. Using appropriate surface treatments thrombogenicity of Nitinol can be manipulated to satisfy both the requirements for stents and defect closures.

In vitro corrosion study by EIS of an equiatomic NiTi alloy and an implant quality AISI 316 stainless steel.

The electrochemical impedance spectroscopy (EIS) technique was used for the study of the electrochemical behavior of an equiatomic NiTi alloy and an implant quality AISI 316 stainless steel type ASTM F138. Experiments were carried out using four different different test solutions: phosphate buffered saline (PBS), Dulbecco minimum essential medium (MEM), MEM + fetal calf serum (FCS), and MEM + fetal calf serum + fibroblast cell (CELL). Specimens were finished to 600-grit SiC paper and were tested in conditions that did not provoke abrupt mechanical damage of the passive film. Bode-phase spectra showed the presence of two maxima and were fitted with an equivalent circuit characterized by two parallel combinations (R, resistance; CPE, constant phase element). The R(1) and CPE(1) branch was assigned to the inner compact passive film and the R(2) and CPE(2) branch to the external porous film. The resistance of the inner film R(1), roughly corresponding to the polarization resistance (R(p)), which is inversely proportional to the material's corrosion rate, increased with the immersion time and was generally greater in PBS than in other media. With the exception of FCS solution, R(1) for NiTi alloy is better or similar to that of ASTM F138.

In vitro corrosion study by EIS of a nickel-free stainless steel for orthopaedic applications.

The electrochemical impedance spectroscopy (EIS) technique was used for the study of the electrochemical behaviour of Ni-free austenitic stainless steel for orthopaedic applications. Experiments were carried out using four different test solutions: (i) phosphate-buffered saline (PBS), (ii) minimum essential medium (MEM), (iii) MEM + 10% fetal calf serum (FCS), (iv) MEM + 10% fetal calf serum + L929 fibroblast cell line (Cell). Bode-phase spectra showed the presence of two maxima and were fitted with an equivalent circuit characterized by two parallel combinations (Resistance, Constant Phase Element). The (R(1), CPE(1)) branch was assigned to the inner compact passive film and the (R(2), CPE(2)) branch to the external porous film. The resistance of the inner film R(1), here directly related to the material's uniform corrosion resistance, raised with the immersion time and increased in the following order: PBS

Titanium for osteointegration: Comparison between a novel biomimetic treatment and commercially exploited surfaces.

The objective of this preliminary in vitro biological study was to assess the effect of the surface physicochemical and topographical properties of a novel bioactive titanium (BSP) obtained by BioSpark treatment. A short-term study was per-formed to evaluate the bone cell response to BSP and compare it to two commercially available materials: no treated (TI) and chemically etched (ETC) titanium. Material characterization was carried out using scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), non-contact laser profilometry (LPM), and Thin Film X-ray Diffraction (TF-XRD). Surface analysis showed ETC to have the highest rough surface, followed by TI surface and then BSP being the smoothest material at micro level, but showing a sub micrometer porous structure covered with a ""net-like"" rough structure. The BSP surface was found to consist of a layer of amorphous calcium and phosphorus and crystalline titanium oxide, not detected in the other materials tested. Indirect biological cytotoxicity studies were performed to determine cell viability following incubation with the eluted extract of the materials. Results indicated no remarkable deterioration in cell viability. In particular, no detectable effect was observed on cellular viability as a result of the chemical interaction between the BSP bioactive surface and the surrounding culture medium. Direct cellular studies showed that the material surface resulted in good cell adhesion on BSP samples. This could be related to both the nano-roughness, and also the crystallinity of the superficial layer of titanium oxide coupled with bioactive Ca- and P-chemical enrichment. The cellular proliferation analysis demonstrated a remarkably higher activity for the cells cultured on BSP, with values significantly higher than the other test materials and the control for all time points. These findings are highly suggestive that the surface properties of the BioSpark treated titanium significantly increases cell proliferation rate. In conclusion, this study has demonstrated that the novel bioactive treatment shows potential as a method for improving osteointegration properties of titanium for orthopaedic and dental implants. (Journal of Applied Biomaterials & Biomechanics 2004; 2: 35-44).

Histomorphometric and microhardness assessments of sheep cortical bone surrounding titanium implants with different surface treatments.

Several factors influence the healing process and the long-term mechanical stability of cementless fixed implants, such as bone remodeling and mineralization processes. Histomorphometric and bone hardness measurements were taken in implants inserted in sheep femoral cortical bone at different times to compare the in vivo osseointegration of titanium screws (diam.; 3.5 x 7 mm length) with the following surface treatments: machined (Ti-MA); acid-etched (Ti-HF); HA vacuum plasma spray (Ti-HA); and Ca-P anodization followed by a hydrothermal treatment (Ti-AM/HA). Ti-MA and Ti-AM/HA implants presented the lowest (Ra = 0.20 +/- 0.01 microm) and highest (Ra = 1.97 +/- 0.64 microm) significant (p < 0.0005) roughness value, respectively. Bone-to-implant contact of Ti-HF was lower than that of the other surface treatments at both experimental times (8 weeks: -20%, ns; 12 weeks: -30%, p < 0.01). Significant differences in MAR (mineral apposition rate) were also found between the different experimental times for Ti-MA (115%, p < 0.01) and Ti-HF (57%, p < 0.01), demonstrating that bone growth had slowed inside the screw threads of Ti-HA and Ti-AM/HA after 12 weeks. No bone microhardness changes in preexisting host bone were found, while Ti-MA showed the lowest value for the inner thread area at 8 weeks (HV(200 microm)= 49.8 +/- 3.8 HV). These findings confirm that osseointegration may be accelerated by adequate surface roughness and bioactive ceramic coating such as Ca-P anodization followed by a hydrothermal treatment, which enhance bone interlocking and mineralization.

Effect of chemical etching and aging in boiling water on the corrosion resistance of Nitinol wires with black oxide resulting from manufacturing process.

The effect of chemical etching in a HF/HNO(3) acid solution and aging in boiling water on the corrosion resistance of Nitinol wires with black oxide has been evaluated with the use of potentiodynamic, modified potentiostatic ASTM F746, and scratch tests. Scanning-electron microscopy, elemental XPS, and Auger analysis were employed to characterize surface alterations induced by surface treatment and corrosion testing. The effect of aging in boiling water on the temperatures of martensitic transformations and shape recovery was evaluated by means of measuring the wire electroresistance. After corrosion tests, as-received wires revealed uniformly cracked surfaces reminiscent of the stress-corrosion-cracking phenomenon. These wires exhibited negative breakdown potentials in potentiostatic tests and variable breakdown potentials in potentiodynamic tests (- 100 mV to + 400 mV versus SCE). Wires with treated surfaces did not reveal cracking or other traces of corrosion attacks in potentiodynamic tests up to + 900-1400-mV potentials and no pitting after stimulation at + 800 mV in potentiostatic tests. They exhibited corrosion behavior satisfactory for medical applications. Significant improvement of corrosion parameters was observed on the reverse scans in potentiodynamic tests after exposure of treated wires to potentials > 1000 mV. In scratch tests, the prepared surfaces repassivated only at low potentials, comparable to that of stainless steel. Tremendous improvement of the corrosion behavior of treated Nitinol wires is associated with the removal of defect surface material and the growth of stable TiO(2) oxide. The role of precipitates in the corrosion resistance of Nitinol-scratch repassivation capacity in particular-is emphasized in the discussion.

Surface conditions of Nitinol wires, tubing, and as-cast alloys. The effect of chemical etching, aging in boiling water, and heat treatment.

The surface conditions of Nitinol wires and tubing were evaluated with the use of X-ray photoelectron spectroscopy, high-resolution Auger spectroscopy, electron backscattering, and scanning-electron microscopy. Samples were studied in the as-received state as well as after chemical etching, aging in boiling water, and heat treatment, and compared to a mechanically polished 600-grit-finish Nitinol surface treated similarly. General regularities in surface behavior induced by the examined surface treatments are similar for wires, tubing, and studied as-cast alloy, though certain differences in surface Ni concentration were observed. Nitinol wires and tubing from various suppliers demonstrated great variability in Ni surface concentration (0.5-15 at.%) and Ti/Ni ratio (0.4-35). The wires in the as-received state, with the exception of those with a black oxide originating in the processing procedure, revealed nickel and titanium on the surface in both elemental and oxidized states, indicating a nonpassive surface. Shape-setting heat treatment at 500 degrees C for 15 min resulted in tremendous increase in the surface Ni concentration and complete Ni oxidation. Preliminary chemical etching and boiling in water successfully prevented surface enrichment in Ni, initially resulting from heat treatment. A stoichiometric uniformly amorphous TiO(2) oxide generated during chemical etching and aging in boiling water was reconstructed at 700 degrees C, revealing rutile structure.

A novel biomimetic treatment for an improved osteointegration of titanium.

Direct osteointegration of titanium and titanium alloys implants is one of the main goals of biomaterials research for dental and orthopedic applications. Chemical, mechanical or biological treatments are investigated searching for fast and durable implant to bone bonding. The aim of the present work is to assess the in vitro mineralisation capabilities and to investigate the mechanical and physico-chemical properties of a new biomimetic treatment on titanium. The new surface treatment was obtained using Anodic Spark Deposition technique, and consists of a first ASD treatment performed in solutions containing phosphate ions followed by a second ASD treatment in a solution rich in calcium ions. The resulting surface is finally treated by alkali etching. The physio-chemical and mechanical properties of this material are analyzed and the mineralization potential is considered by surface analysis after soaking it in different solutions of simulated body fluid (SBF). The developed biomimetic treatment was then compared to other treatments from the literature. The proposed treatment was found to possess a very high mineralization capaci-ty, that makes its application very interesting in terms of speed and strength of direct implant osteointegration. (Journal of Ap-plied Biomaterials & Biomechanics 2003; 1: 33-42).

Osseointegration of sandblasted or anodised hydrothermally-treated titanium implants: mechanical, histomorphometric and bone hardness measurements.

The improvement of the implant-bone interface is still an open problem in the long-term mechanical stability of cementless fixed implants. Mechanical, histomorphometric and bone hardness measurements were performed in sheep femoral cortical bone implants at 8 and 12 weeks from surgery to compare in vivo the osseointegration of titanium screws (psi 3.5 mm x 7 mm length) with two different surface treatments: sandblasting with 70-100 microm HA followed by acid etching with HNO3 (Group A) and Ca-P anodization followed by a hydrothermal treatment (Group B). No significant differences were found for maximum push-out force and interfacial strength between groups at both experimental times. No significant difference was observed for Bone Ingrowth between groups at both experimental times, while the Affinity Index of Group B was significantly higher (7.5%, p<0.05) and lower (10.2%, p<0.05) than that of Group A at 8 and 12 weeks, respectively. Finally, a significant increase in bone microhardness measured within 200 microm from the interface and inside the thread depth of Group A was observed between the two experimental times (p<0.05). In conclusion, present findings show that osseointegration may be accelerated by adequate surface roughness and bioactive ceramic coating such as current tested treatments which enhance bone interlocking and mineralization.

Effect of copper on the localized corrosion resistance of Ni-Ti shape memory alloy.

An electrochemical study aiming at the evaluation of corrosion parameters using potentiodynamic and potentiostatic techniques ("scratch" and modified ASTM F746) was conducted in 0.9% NaCl on wires from equiatomic Ni-Ti and ternary Ni44Ti51Cu5 superelastic alloys with Ti90Mo10 as a reference material. The results obtained using potentiostatic tests, that simulate better the behavior of material in service conditions than potentiodynamic ones, indicate that both Ni-Ti and Ni-Ti-Cu wires exhibit low corrosion potentials (approximately 50-150 mV versus SCE) inferior to that of Ti-Mo alloy. The latter proved to be immune to localized corrosion attacks up to 800 mV.

Evaluation by electrochemical tests of the passive film stability of equiatomic Ni-Ti alloy also in presence of stress-induced martensite.

In this study, potentiodynamic polarization scans, potentiostatic scratch tests, and modified American Society for Testing and Materials F746 tests were carried out in simulated body fluids on commercial orthodontic wires made of different classes of materials and on titanium used as a reference. The stability of passivating film, evaluated by electrochemical techniques that abruptly damage it, e.g., potentiostatic scratch test, increased in the following order: Ni-Ti

In vitro and in vivo behaviour of Ca- and P-enriched anodized titanium.

The influence of different surface preparations on titanium biocompatibility and bone integration was evaluated. Commercially grade 2 titanium rods (diameter 2 mm, length: 3 mm), vacuum annealed and hydrofluoric acid etched was selected for its promising surface characteristics to achieve good direct osseointegration. Some rods were surface modified by Anodic Spark Discharge anodization and a thin layer (approximately 5 microm) of amorphous TiO2 containing Ca and P (Ti/AM) was obtained. Some of the Ti/AM specimens underwent a further hydrothermal treatment to produce a thin outermost layer (approximately 1 microm) of hydroxyapatite (Ti/AM/HA). Cytotoxicity tests (direct contact: ISO 10993-5) showed good cytocompatibility for all tested samples. Ti and tissue culture substrate + DMEM control, respectively, were associated with a significant higher proportion of attached cells than Ti/AM and Ti/AM/HA (P < 0.0005), but this was in the normal range of 10-20% of unattached cells for cytocompatible materials. Histomorphometric analysis conducted on samples inserted in the cancellous bone of distal femoral epiphysis of Sprague-Dawley rats gave the following results at 4 and 8 weeks: Affinity index (AI%) data proving the surface osteconductive properties of non-anodized acid etched Ti (AI-4 weeks: 67.1 +/- 17.0%; AI-8 weeks: 74.8 +/- 11.5%). Ti/AM samples showed the lowest values (AI-4 weeks: 45.8 +/- 15.9%; AI-8 weeks: 68.5 +/- 13.6%) while the best performances of the Ti/AM/HA samples (AI-4 weeks: 60.4 +/- 21.8%; AI-8 weeks: 79.5 + 9.37%) indicated that hydroxyapatite allowed a higher bone to implant contact respect to Ti only. Further investigations should be performed in order to better understand the mechanism of observed in vitro behaviour and to achieve information on long-term osseointegration process.

Localized corrosion behaviour in simulated human body fluids of commercial Ni-Ti orthodontic wires.

The corrosion performances in simulated human body fluids of commercial equiatomic Ni-Ti orthodontic wires having various shape and size and produced by different manufacturers were evaluated; for comparison purposes wires made of stainless steel and of cobalt-based alloy were also examined. Potentiodynamic tests in artificial saliva at 40 degrees C indicated a sufficient pitting resistance for the Ni-Ti wires, similar to that of cobalt-based alloy wire; the stainless steel wire, instead, exhibited low pitting potential. Potentiodynamic tests at 40 degrees C in isotonic saline solution (0.9% NaCl) showed, for Ni-Ti and stainless steel wires, pitting potential values in the range approximately 200-400 mV and approximately 350 mV versus SCE, respectively: consequently, according to literature data (Hoar TP, Mears DC. Proc Roy Soc A 1996;294:486-510), these materials should be considered potentially susceptible to pitting; only the cobalt-based alloy should be immune from pitting. The localized corrosion potentials determined in the same environment by the ASTM F746 test (approximately 0-200 mV and 130 mV versus SCE for Ni-Ti and stainless steel, respectively) pointed out that for these materials an even higher risk of localized corrosion. Slight differences in localized corrosion behaviour among the various Ni-Ti wires were detected.

Effect of different surface finishing and of hydroxyapatite coatings on passive and corrosion current of Ti6Al4V alloy in simulated physiological solution.

Direct and alternating current electrochemical tests were carried out on Ti6Al4V with different surface finishing and with hydroxyapatite (HA) coatings. Sand-blasting and rough titanium deposits obtained by vacuum plasma spraying (VPS) bring about an increase of passive and corrosion current density (c.d.) with respect to smooth Ti6Al4V, as a consequence of the augmentation of the real surface. The presence of HA deposits obtained by VPS causes an increase of passive and corrosion c.d. of the metallic substrate of about one order of magnitude and this should be taken into account in view of human body applications.

Corrosion resistance tests on NiTi shape memory alloy.

The corrosion performances of NiTi shape memory alloys (SMA) in human body simulating fluids were evaluated in comparison with other implant materials. As for the passivity current in potentiostatic conditions, taken as an index of ion release, the values are about three times higher for NiTi than for Ti6Al4V and austenitic stainless steels. Regarding the localized corrosion, while plain potentiodynamic scans indicated for NiTi alloy good resistance to pitting attack similar to Ti6Al4V, tests in which the passive film is abruptly damaged (i.e. potentiostatic scratch test and modified ASTM F746) pointed out that the characteristics of the passive film formed on NiTi alloy (whose strength can be related to the alloy's biocompatibility) are not as good as those on Ti6Al4V but are comparable or inferior to those on austenitic stainless steels.

Duplex stainless steels for osteosynthesis devices.

The austenitic stainless steels used today for the manufacture of osteosynthesis devices are sensitive to crevice corrosion. In this study the corrosion properties of some duplex stainless steels were evaluated and compared to traditional austenitic stainless steels. According to our results the following ranking was established: 23Cr-4Ni less than AISI 316L less than ASTM F138 less than 22Cr-5Ni-3Mo less than 27Cr-31Ni-3.5Mo less than 25Cr-7Ni-4Mo-N. In particular the results showed that the high-performance 25Cr-7Ni-4Mo-N duplex stainless steel, with high molybdenum and nitrogen contents, can be considered not susceptible to crevice corrosion in the human body. The duplex stainless steels have also better mechanical properties at the same degree of cold working compared with austenitic stainless steels. Hence the 25Cr-7Ni-4Mo-N duplex stainless steel can be considered a convenient substitute of ASTM F138 for orthopedic and osteosynthesis devices.