Electrochemical stability and corrosion resistance of Ti-Mo alloys for biomedical applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development of Ti-Mo alloys for biomedical applications: Microstructure and electrochemical characterization

Ti-Mo alloys from 4 to 20 Mo wt.% were arc-melted. Their compositions and surfaces were analyzed by EDX, XRF and SEM. The Mo mapping shows a homogeneous distribution for all alloys. The XRD analysis showed that the crystal structure of the alloys is sensitive to the Mo concentration; a mixture of the hexagonal alpha' and orthorhombic alpha '' phases was observed for the Ti-4Mo alloy, and the alpha '' phase is observed almost exclusively when the concentration of Mo added to the Ti reaches 6%. A significant retention of the beta phase is observed for the alloy containing 10% Mo, while at higher Mo concentrations (15% and 20%), retention of phase beta is only verified. Preliminary electrochemical studies have indicated a valve-metal behavior and good corrosion resistance in aerated Ringer solution for all alloys. (c) 2006 Published by Elsevier B.V.

Modificação de superfície empregando-se laser e recobrimento de implantes dentários de titânio com apatitas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Assessment of biodegradable magnesium alloys for enhanced mechanical and biocompatible properties

Biomaterials have been used for more than a century in the human body to improve body functions and replace damaged tissues. Currently approved and commonly used metallic biomaterials such as, stainless steel, titanium, cobalt chromium and other alloys have been found to have adverse effects leading in some cases, to mechanical failure and rejection of the implant. The physical or chemical nature of the degradation products of some implants initiates an adverse foreign body reaction in the tissue. Some metallic implants remain as permanent fixtures, whereas others such as plates, screws and pins used to secure serious fractures are removed by a second surgical procedure after the tissue has healed sufficiently. However, repeat surgical procedures increase the cost of health care and the possibility of patient morbidity. This study focuses on the development of magnesium based biodegradable alloys/metal matrix composites (MMCs) for orthopedic and cardiovascular applications. The Mg alloys/MMCs possessed good mechanical properties and biocompatible properties. Nine different compositions of Mg alloys/MMCs were manufactured and surface treated. Their degradation behavior, ion leaching, wettability, morphology, cytotoxicity and mechanical properties were determined. Alloying with Zn, Ca, HA and Gd and surface treatment resulted in improved mechanical properties, corrosion resistance, reduced cytotoxicity, lower pH and hydrogen evolution. Anodization resulted in the formation of a distinct oxide layer (thickness 5-10 μm) as compared with that produced on mechanically polished samples (~20-50 nm) under ambient conditions. It is envisaged that the findings of this research will introduce a new class of Mg based biodegradable alloys/MMCs and the emergence of innovative cardiovascular and orthopedic implant devices.^

Histomorphologic evaluation of Ti-13Nb-13Zr alloys processed via powder metallurgy. A study in rabbits

This study presents the in-vivo evaluation of Ti-13Nb-13Zr alloy implants obtained by the hydride route via powder metallurgy. The cylindrical implants were processed at different sintering and holding times. The implants` were characterized for density, microstructure (SEM), crystalline phases (XRD), and bulk (EDS) and surface composition (XPS). The implants were then sterilized and surgically placed in the central region of the rabbit`s tibiae. Two double fluorescent markers were applied at 2 and 3 weeks, and 6 and 7 weeks after implantation. After an 8-week healing period, the implants were retrieved, non-decalcified section processed, and evaluated by electron, UV light (fluorescent labeling), and light microscopy (toluidine blue). BSE-SEM showed close contact between bone and implants. Fluorescent labeling assessment showed high bone activity levels at regions close to the implant surface. Toluidine blue staining revealed regions comprising osteoblasts at regions of newly forming/formed bone close to the implant surface. The results obtained in this study support biocompatible and osseoconductive properties of Ti-13Nb-13Zr processed through the hydride powder route. (c) 2007 Published by Elsevier B.V.

Cytotoxicity study of some Ti alloys used as biomaterial

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of thermal treatments on tensile strength of commercially cast pure titanium and Ti-6Al-4V alloys

Heating titanium structures is assumed to relieve tensions induced by the casting process as well as possibly optimizing some mechanical properties. The aim of this investigation was to evaluate the effect of thermal treatments on tensile strength of commercially pure titanium (CP Ti) and Ti-6Al-4V alloy. Thirty dumbbell rods, with diameters of 3.0 mm at the central segment and lengths of 42 mm, were cast for each metal using the Rematitan System. CP Ti and Ti-6Al-4V specimens were randomly divided into three groups of ten: a control group that received no thermal treatment and two test groups. One (T1) was heated at 750°C for 2 h and the other (T2) was annealed at 955°C for 1 h and aged at 620°C for 2 h. Tensile strength was measured with a universal testing machine (MTS model 810). Tensile strength means and standard deviations were statistically compared using a Kruskal-Wallis test at a α = 0.05 significance level. No statistically significant differences in tensile strength were observed among CP Ti groups. For the Ti-6Al-4V alloy, the control and T1 groups revealed statistically higher tensile strengths when compared to the T2 group, with no significant difference between the control and T1 groups. © 2005 Springer Science + Business Media, Inc.

Indentation size effect and strain rate sensitivity of nanocrystalline Mg-Al alloys

Deformation Behaviour of microcrystalline (mc) and nanocrystalline (nc) Mg-5%Al alloys produced by hot extrusion of ball-milled powders were investigated using instrumented indentation tests. The hardness values of the mc and nc metals exhibited indentation size effect (ISE), with nc alloys showing weaker ISE. The highly localized dislocation activities resulted in a small activation volume, hence enhanced strain rate sensitivity. Relative higher strain rate sensitivity and the negative Hall-Petch Relationship suggested the increasingly important role of grain boundary mediated mechanisms when the grain size decreased to nanometer region.

Compressive behaviour of nanocrystallilne Mg-5%Al alloys

Magnesium alloys are attracting increasing research interests due to their low density, high specific strength and good mechineability and availability as compared to other structural materials. However, the deformation and failure mechanisms of nanocrystalline Mg alloys have not been well understood. In this work, the deformation behavior of nanocrystalline Mg-5% Al alloys was investigated using compression test, with a focus on the effects of grain size. The average grain size of the Mg-Al alloy was changed from 13 µm to 50 nm via mechanical milling. The results showed that grain size had a significant influence on the yield stress and ductility of the Mg alloys, and the materials exhibited increased strain rate sensitivity with decrease of grain size. The deformation mechanisms were also strongly dependent with the grain sizes.

Deformation behaviours of coarse-grained and nanocrystalline Mg-5wt% Al alloys

Magnesium alloys have been of growing interest to various engineering applications, such as the automobile, aerospace, communication and computer industries due to their low density, high specific strength, good machineability and availability as compared with other structural materials. However, most Mg alloys suffer from poor plasticity due to their Hexagonal Close Packed structure. Grain refinement has been proved to be an effective method to enhance the strength and alter the ductility of the materials. Several methods have been proposed to produce materials with nanocrystalline grain structures. So far, most of the research work on nanocrystalline materials has been carried out on Face-Centered Cubic and Body-Centered Cubic metals. However, there has been little investigation of nanocrystalline Mg alloys. In this study, bulk coarse-grained and nanocrystalline Mg alloys were fabricated by a mechanical alloying method. The mixed powder of Mg chips and Al powder was mechanically milled under argon atmosphere for different durations of 0 hours (MA0), 10 hours (MA10), 20 hours (MA20), 30 hours (MA30) and 40 hours (MA40), followed by compaction and sintering. Then the sintered billets were hot-extruded into metallic rods with a 7 mm diameter. The obtained Mg alloys have a nominal composition of Mg–5wt% Al, with grain sizes ranging from 13 μm down to 50 nm, depending on the milling durations. The microstructure characterization and evolution after deformation were carried out by means of Optical microscopy, X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Scanning Probe Microscopy and Neutron Diffraction techniques. Nanoindentaion, compression and micro-compression tests on micro-pillars were used to study the size effects on the mechanical behaviour of the Mg alloys. Two kinds of size effects on the mechanical behaviours and deformation mechanisms were investigated: grain size effect and sample size effect. The nanoindentation tests were composed of constant strain rate, constant loading rate and indentation creep tests. The normally reported indentation size effect in single crystal and coarse-grained crystals was observed in both the coarse-grained and nanocrystalline Mg alloys. Since the indentation size effect is correlated to the Geometrically Necessary Dislocations under the indenter to accommodate the plastic deformation, the good agreement between the experimental results and the Indentation Size Effect model indicated that, in the current nanocrystalline MA20 and MA30, the dislocation plasticity was still the dominant deformation mechanism. Significant hardness enhancement with decreasing grain size, down to 58 nm, was found in the nanocrystalline Mg alloys. Further reduction of grain size would lead to a drop in the hardness values. The failure of grain refinement strengthening with the relatively high strain rate sensitivity of nanocrystalline Mg alloys suggested a change in the deformation mechanism. Indentation creep tests showed that the stress exponent was dependent on the loading rate during the loading section of the indentation, which was related to the dislocation structures before the creep starts. The influence of grain size on the mechanical behaviour and strength of extruded coarse-grained and nanocrystalline Mg alloys were investigated using uniaxial compression tests. The macroscopic response of the Mg alloys transited from strain hardening to strain softening behaviour, with grain size reduced from 13 ìm to 50 nm. The strain hardening was related to the twinning induced hardening and dislocation hardening effect, while the strain softening was attributed to the localized deformation in the nanocrystalline grains. The tension–compression yield asymmetry was noticed in the nanocrystalline region, demonstrating the twinning effect in the ultra-fine-grained and nanocrystalline region. The relationship k tensions < k compression failed in the nanocrystalline Mg alloys; this was attributed to the twofold effect of grain size on twinning. The nanocrystalline Mg alloys were found to exhibit increased strain rate sensitivity with decreasing grain size, with strain rate ranging from 0.0001/s to 0.01/s. Strain rate sensitivity of coarse-grained MA0 was increased by more than 10 times in MA40. The Hall-Petch relationship broke down at a critical grain size in the nanocrystalline region. The breakdown of the Hall-Petch relationship and the increased strain rate sensitivity were due to the localized dislocation activities (generalization and annihilation at grain boundaries) and the more significant contribution from grain boundary mediated mechanisms. In the micro-compression tests, the sample size effects on the mechanical behaviours were studied on MA0, MA20 and MA40 micro-pillars. In contrast to the bulk samples under compression, the stress-strain curves of MA0 and MA20 micro-pillars were characterized with a number of discrete strain burst events separated by nearly elastic strain segments. Unlike MA0 and MA20, the stress-strain curves of MA40 micro-pillars were smooth, without obvious strain bursts. The deformation mechanisms of the MA0 and MA20 micro-pillars under micro-compression tests were considered to be initially dominated by deformation twinning, followed by dislocation mechanisms. For MA40 pillars, the deformation mechanisms were believed to be localized dislocation activities and grain boundary related mechanisms. The strain hardening behaviours of the micro-pillars suggested that the grain boundaries in the nanocrystalline micro-pillars would reduce the source (nucleation sources for twins/dislocations) starvation hardening effect. The power law relationship of the yield strength on pillar dimensions in MA0, MA20 supported the fact that the twinning mechanism was correlated to the pre-existing defects, which can promote the nucleation of the twins. Then, we provided a latitudinal comparison of the results and conclusions derived from the different techniques used for testing the coarse-grained and nanocrystalline Mg alloy; this helps to better understand the deformation mechanisms of the Mg alloys as a whole. At the end, we summarized the thesis and highlighted the conclusions, contributions, innovations and outcomes of the research. Finally, it outlined recommendations for future work.

Biomaterials in orthopedic bone plates : a review

This paper aims to review biomaterials used in manufacturing bone plates including advances in recent years and prospect in the future. It has found among all biomaterials, currently titanium and stainless steel alloys are the most common in production of bone plates. Other biomaterials such as Mg alloys, Ta alloys, SMAs, carbon fiber composites and bioceramics are potentially suitable for bone plates because of their advantages in biocompatibility, bioactivity and biodegradability. However, today either they are not used in bone plates or have limited applications in only some flexible small-size implants. This problem is mainly related to their poor mechanical properties. Additionally, production processes play an effective role. Therefore, in the future, further studies should be conducted to solve these problems and make them feasible for heavy-duty bone plates.

Compressive behaviour of nanocrystalline Mg-5Al alloys

Magnesium alloys are attracting increasing research interests due to their low density, high specific strength, good machinability and availability as compared to other structural materials. However, the deformation and failure mechanisms of nanocrystalline (nc) Mg alloys have not been well understood. In this work, the deformation behaviour of nc Mg-5Al alloys was investigated using compression test, with focus on the effects of grain size. The average grain size of the Mg- Al alloy was changed from 13 to 50 nm via mechanical milling. The results showed that grain size had a significant influence on the yield stress and ductility of the Mg alloys, and the materials exhibited increased strain rate sensitivity with a decrease in grain size. The deformation mechanisms were also strongly dependent on the grain sizes.

Orthopedic bone plates : evolution in structure implementation technique and biomaterial

With many important developments over the last century, nowadays orthopedic bone plate now excels over other types of internal fixators in bone fracture fixation. The developments involve the design, material and implementation techniques of the plates. This paper aims to review the evolution in implementation technique and biomaterial of the orthopedic bone plates. Plates were initially used to fix the underlying bones firmly. Accordingly, Compression plate (CP), Dynamic compression plate (DCP), Limited contact dynamic compression plate (LC-DCP) and Point contact fixator (PC-Fix) were developed. Later, the implementation approach was changed to locking, and the Less Invasive Stabilization System (LISS) plate was introduced as a result. Finally, a combination of both of these approaches has been used by introducing the Locking Compression Plate (LCP). Currently, precontoured LCPs are mainly used for bone fracture fixation. In parallel with structure and implementation techniques, numerous advances have occurred in biomaterials of the plates. Titanium and stainless steel alloys are now the most common biomaterials in production of orthopedic bone plates. However, regarding the biocompatibility, bioactivity and biodegradability characteristics of Mg alloys, Ta alloys, SMAs, carbon fiber composites and bioceramics, these materials are considered as potentially suitable for plates. However, due to poor mechanical properties, they have very limited applications. Therefore, further studies are required in future to solve these problems and make them feasible for heavy-duty bone plates.

Supramolecular selection in molecular alloys

Complexes of the type \[M(phen)3](PF6)2 (M = Ni(II), Fe(II), Ru(II) and phen = 1,10-phenanthroline) were found to co-crystallize to form molecular alloys (solid solutions of molecules) with general formula \[MAxMB1–x(phen)3](PF6)2·0.5H2O in which the relative concentrations of the metal complexes in the crystals closely match those in the crystallizing solution. Consequently, the composition of the co-crystals can be accurately predicted and controlled by modulating the relative concentrations of the metal complexes in the crystallizing solution. Although they are chemically and structurally similar, complexes of the type \[M(bipy)3](PF6)2 (M = Ni(II), Fe(II), Ru(II) and bipy = 2,2′-bipyridine) display markedly different behavior upon co-crystallization. In this case, the resulting co-crystals of general formula \[MAxMB1–x(bipy)3](PF6)2 have relative concentrations of the constituent complexes that are markedly different from the relative concentrations of the complexes initially present in the crystallizing solution. For example, when the nickel and iron complexes are co-crystallized from a solution containing a 50:50 ratio of each, the result is the formation of some crystals with a higher proportion of iron and others with a higher proportion of nickel. The relative concentrations of the metal complexes in the crystals can vary from those in the crystallizing solutions by as much as 15%. This result was observed for a range of combinations of metal complexes (Ni/Fe, Ni/Ru, and Fe/Ru) and a range of starting concentrations in the crystallizing solutions (90:10 through to 10:90 in 10% increments). To explain this remarkable result, we introduce the concept of “supramolecular selection”, which is a process driven by molecular recognition that leads to the partially selective aggregation of like molecules during crystallization.