New chemical treatment for bioactive titanium alloy with high corrosion resistance

It was recently claimed that titanium metal and its alloys can bond to the living bone, without being coated by apatite (VPS coatings), but by being chemically and heat-treated. The bioactivity of treated titanium is of interest because of the opportunity to obtain orthopaedic or dental implants presenting, at the same time, high toughness, strength and fatigue resistance as well as bone-bonding ability. The bioactive behaviour of the treated implants is due to the presence of a modified surface, which, during soaking in body fluid, promotes the precipitation of apatite. The apatite formed is strongly bonded to the substrate and promotes living bone bonding. In this work were characterised samples of Ti-6Al-7Nb alloy with surfaces presenting a different chemical and mechanical state. The aim of the research was twofold. The first objective was to characterise chemically and heat-treated samples with different surface topography, in order to define the best conditions for osteogenic integration. The second aim was to assess the corrosion behaviour of the bioactive implants, because they expose a microporous and quite thin modified surface layer. No-treated and passivated samples, with a surface state closed to that nowadays used on implants, were used as reference. The surface structure, morphology, electrochemical behaviour and bioactivity of the different samples were assessed by means of XRD, SEM-EDS, anodic polarizations, open circuit measurements and in-vitro tests. Results evidence that it is possible to modify the surface of the Ti-6Al-7Nb alloy in order to obtain the formation of a bioactive layer and that the substrate roughness influences the characteristics of the surface layer formed. It was also evidenced that the as treated surfaces present inadequate corrosion behaviour, so a new two-step chemical treatment has been developed in order to obtain a bioactive material with good corrosion resistance.     

Variation of roughness and adhesion strength of deposited apatite layers on titanium dental implants

It is known that surface roughness and chemical composition of the titanium surface influence the osseointegration of titanium implants. Most commercial dental implants offer a shot-blasted rough surface. It is also known that apatite layers coating the surface of titanium implants improve bone response, but the adhesion of the layer to the substrate poses some problems.In this study the roughness and adhesion strength to a titanium dental implant surface of an apatite layer deposited via wet chemistry after a thermochemical treatment were compared with those of plasma-sprayed apatite layers and machined titanium surfaces. Different surface conditions have been studied: (a) as-received machined dental implant surface; (b) grit-blasted titanium surface; (c) grit-blasted and thermochemically-treated titanium surface; (d) titanium surfaces coated with plasma-sprayed apatite. The morphology and roughness of the samples were measured and compared. The adhesion of the apatite layers to the titanium was compared by means of a scratch test.Measured roughness showed that the deposition of an apatite layer did not affect roughness but plasma-sprayed apatite produced a decrease on roughness values when compared to control samples. Both roughness and adhesion strength of the deposited apatite layer to the titanium substrate were higher than those of the plasma-sprayed apatite.     

Designing,processing and characterisation of titanium cylinders with graded porosity: An alternative to stress-shielding solutions

Bone resorption events and consequent failure of titanium implants are frequently related to stress-shielding problems, due to stiffness mismatch with respect to bone. This is a mechanical incompatibility problem, which is difficult to resolve because of the challenge of replacing highly anisotropic biomechanical systems, as is the case of dental implants. This work describes the designing, processing and characterisation of cylindrical titanium samples with a longitudinally graded porosity obtained by conventional powder-metallurgy techniques. The design concept used was biomimetic, based on the stiffness properties of the tissues to be in contact with titanium dental implants. Processing conditions were optimised in terms of different parameters: structural integrity, porosity and mechanical properties. The influence of sintering temperature was evaluated in search of optimum results under the above criteria. The behaviour of longitudinal porosity and Young’s modulus were consistent with the preliminary design concept from the original biomechanical system. Mechanical strength results were reasonably suitable for dental applications and they were favourably sensitive to increasing sintering temperature, due to a stronger adhesion between initial green layers of cylindrical samples. Results showed that it is possible to obtain a desired longitudinal gradient in Young’s modulus, as well as suitable yield strength values. The optimised processing described suggests that it is a plausible candidate for manufacturing dental implants with a good balance between reduced stress shielding and suitable mechanical strength, which encourages us to undertake further work along the same lines.     

The role of metal–ceramic interfaces on the high temperature mechanical response of nanostructured nickel–yttria tetragonal zirconia polycrystals (Ni–YTZP)

High temperature creep of a metal–ceramic composite consisted of yttria tetragonal zirconia polycrystals (YTZP) with a certain amount of nickel grains (Ni–YTZP, 2.5% vol.) has been studied. The average grain size of YTZP grains was 0.20 μm, whereas that of the Ni grains was 50–70 nm. This work reports the mechanical response under creep of such composite materials. It is found that the activation energy for creep is significantly higher than that reported in similar systems with much larger nickel grains. This fact has been explained in terms of the chemical nature of the metal–ceramic interfaces.     

Oxidized nickel–titanium foams for bone reconstructions: chemical and mechanical characterization

This work examines NiTi foams that have been treated using a new oxidation treatment for obtaining Ni-free surfaces that could allow the ingrowth of living tissue, thereby increasing the mechanical anchorage of implants. A significant increase in the real surface area of these materials can decrease corrosion resistance and favour the release of Ni. This chemical degradation can induce allergic reactions or toxicity in the surrounding tissues. This study determines the porosity, surface characteristics, phase transformation, mechanical properties, corrosion behaviour and Ni release into the simulated body fluid medium of foams treated by a new surface oxidation treatment that produces Ni-free surfaces. These foams have pores in an appropriate range of sizes and interconnectivity, and thus their morphology is similar to that of bone. Their mechanical properties are biomechanically compatible with bone. The titanium oxide on the surface significantly improves corrosion resistance and decreases nickel ion release, while barely affecting transformation temperatures.     

Surface analysis and osteoblasts response of a titanium oxi-carbide film deposited on titanium by ion plating plasma assisted (IPPA)

Titanium is the most widely used material in orthopaedic and dental implantoprosthesis due to its superior physical properties and enhanced biocompatibility due to the spontaneous formation of a passivating layer of titanium oxides which, however, does not form good chemical bonds with bone and tends to brake exposing bulk titanium to harsh body fluids releasing titanium particles which may prime an inflammation response and a fibrotic tissue production. In order to avoid these possible problems and to enhance the biocompatibility of titanium implants, modifications of titanium surfaces by many different materials as hydroxyapatite, titanium nitride, titanium oxide and titanium carbide have been proposed. The latter is shown to be an efficient protection for the titanium implant in the harsh conditions of biological tissues and, compared to untreated titanium, acting like an osteoblast stimulation factor increasing in vitro production of proteins involved in osteogenesis. These results were confirmed by in vivo experiments in rabbits: implants covered by the titanium carbide (TiC) layer were faster and better osseointegrated than untreated titanium implants. The TiC layer was deposited by a Pulsed Laser Deposition (PLD) device which allowed only one deposition per cycle, shown to be unsuitable for industrial applications. Therefore the main objective of the present work was to replace PLD process with an Ion Plating Plasma Assisted (IPPA) deposition process, which is suitable for industrial upgrading. By this technique, nanostructured TiOx-TiCy-C has been deposited on titanium after sandblasting with 120 micron zirconia spheres. XPS analyses revealed the presence of about 33% carbon (50% of which is present as free carbon), 39% oxygen and 28% titanium (37% of which is bound to carbon to form TiC and 63% is bound to oxygen to form non stoichiometric oxides). Surface mechanical response of as-deposited coatings has been performed by nanoindentation techniques. Focused Ion Beam micrographs showed bigger differences on the obtained nanostructure compared to the PLD coating structure; in vitro tests confirm for IPPA produced coatings an improvement in stimulating osteoblasts to produce mRNA's of proteins involved in the ossification process, this latter case they resulted to be faster and more efficient. The proposed treatement is expected to improve the good results obtained by PLD, in vivo as well.     

Surface modification of Ti–6Al–4V alloy for biomineralization and specific biological response: Part I,inorganic modification

Titanium and its alloys represent the gold standard for orthopaedic and dental prosthetic devices, because of their good mechanical properties and biocompatibility. Recent research has been focused on surface treatments designed to promote their rapid osteointegration also in case of poor bone quality. A new surface treatment has been investigated in this research work, in order to improve tissue integration of titanium based implants. The surface treatment is able to induce a bioactive behaviour, without the introduction of a coating, and preserving mechanical properties of Ti6Al4V substrates (fatigue resistance). The application of the proposed technique results in a complex surface topography, characterized by the combination of a micro-roughness and a nanotexture, which can be coupled with the conventional macro-roughness induced by blasting. Modified metallic surfaces are rich in hydroxyls groups: this feature is extremely important for inorganic bioactivity (in vitro and in vivo apatite precipitation) and also for further functionalization procedures (grafting of biomolecules). Modified Ti6Al4V induced hydroxyapatite precipitation after 15 days soaking in simulated body fluid (SBF). The process was optimised in order to not induce cracks or damages on the surface. The surface oxide layer presents high scratch resistance.     

Mechanical examinations on dental implants with porous titanium coating

Due to its good biocompatibility, porous titanium is an interesting material for biomedical applications. Bone tissue can grow inside the porous structure and maintain a long and stable connection between the implant and the human bone. To investigate its long term stability, the mechanical behavior of porous titanium was tested under static and dynamic conditions and was compared to human bone tissue. A promising application of this material is the coating of dental implants. A manufacturing technique was developed and implants were produced. These implants were fatigue tested according to modified ISO 14801 and the micro structural change was examined. The fatigue test was statically modeled using finite element analysis (FEA). The results show that the implants resist a continuous load which is comparable to the loading conditions in the human jaw. The experiments show that the porous titanium has bone-like mechanical properties. Additionally the porous titanium shows an anisotropic behavior of its mechanical properties depending on the alignment of the pores. Finally, other potential applications of porous titanium are outlined.     

Design optimization of functionally graded dental implant for bone remodeling

Despite a great success, one of the key issues facing in dental implantation clinic is a mismatch of mechanical properties between engineered and native biomaterials, which makes osseointegration and bone remodeling problematical. Functionally Graded Material (FGM) has been proposed as a potential upgrade to some conventional implant materials like titanium for selection in prosthetic dentistry. The idea of FGM dental implant is that the property would vary in a certain pattern to match the biomechanical characteristics required at different regions in the hosting bone. However, mating properties do not necessarily guarantee the best osseointegration and bone remodeling. No existing report has been available to develop an optimal design of FGM dental implant for promoting a long-term success. This paper aims to explore this critical issue by using the computational bone remodeling and design optimization. A buccal–lingual sectional model, which consists of a single unit implant and four other adjacent teeth, was constructed from computerized tomography (CT) scan images. Bone remodeling induced by use of various FGM dental implants is calculated over the period of 4 years. Based upon remodeling results, response surface method (RSM) is adopted to develop a multi-objective optimal design for FGM implantation FGM designs.     

Rapid prototyping and rapid manufacturing in medicine and dentistry

The fundamentals and latest developments of Rapid Prototyping (RP) and Rapid Manufacturing (RM) technologies and the application of most common biomaterials such as titanium and titanium alloy (Ti6Al4V) are discussed in this paper. The issues while fabricating pre-surgical models, scaffolds for cell growth and tissue engineering and concerning fabrication of medical implants and dental prostheses are addressed. Major resources related to RP/RM technology, biocompatible materials and RP/RM applications in medicine and dentistry are reviewed. A large number of papers published in leading journals are searched.

Besides the titanium and titanium alloys which were established as bio-compatible materials over five decades ago, other biocompatible materials such as cobalt-chromium and PEEK have also been increasingly used in medical implants and dental prosthesis fabrication. For over a decade RP technologies such as Selective Laser Sintering (SLS) and Selective Laser Melting (SLM) along with the Fused Depositing Modelling (FDM) are predominantly employed in the fabrication of implants, prostheses and scaffolds. Recently Electron Beam Melting (EBM) has been successfully employed for fabrication of medical implants and dental prostheses with complex features. In dentistry crown restoration, the use of thin copings of Ti6Al4V made by the EBM process is an emerging trend. This review is based upon the findings published in highly cited papers during the last two decades. However the major breakthrough in the field of RP/RM for medical implants and dental prostheses took place in the last decade. The fabrication of medical implants and prostheses and biological models have three distinct characteristics: low volume, complex shapes and they are highly customised. These characteristics make them suitable to be made by RM technologies even on a commercial scale. Finally, current status and methodology and their limitations as well as future directions are discussed.     

Ion implantation of titanium based biomaterials

Titanium and its alloys are widely used as implant materials. Their integration in the bone is in general very good without fibrous interface layer. However, titanium and its alloys have certain limitations. Metal ions are released from the implant alloy and have been detected in tissues close to titanium implants. The release of these elements, even in small amounts, may cause local irritation of the tissues surrounding the implant. Cell and tissue responses are affected not only by the chemical properties of the implant surface, but also by the surface topography or roughness of the implants. To overcome the problem of ion release and to improve the biological, chemical, and mechanical properties, many surface treatment techniques are used. Any surface treatment that would elicit favorable response from tissues can be applied to enhance the usefulness of the implants. In view of this, the current review describes surface modification of titanium and titanium alloys by ion beam implantation.     

Al2O3-and ZrO2-modified dental glass ceramics

Castable machinable glass-ceramics have been widely considered as aesthetic materials for dental restoration. In order to extend their applications to bridge-work fabrication, it is necessary to increase their fracture strength and fracture toughness. The effects of ziconia and alumina additions on the properties of glass-ceramics, especially on the mechanical properties were studied. It was found that appropriate addition of alumina increases the bending strength due to aluminium strengthening the glass-ceramic by means of incorporation into the glass network. However, additions of ziconia fail to show promising results on the mechanical property. The evolution of recrystallization and the associated microstructure were also studied and are discussed.     

The properties of a wrought biomedical cobalt-chromium alloy

Two wrought biomedical cobalt-chromium alloys have been developed, and their mechanical properties and corrosion resistance determined by means of tensile and hardness tests and by electrochemical potential-time curves for isolated specimens in a 6.0 wt% NaCl solution at room temperature. In comparison with a current dental alloy, SC-H, and the basic type 18-8 austenitic stainless steel, it is shown that alloy II (chemical composition in wt%:0.11 C, 22.07 Cr, 15.20 Ni, 3.75 Mo, 9.30 W, balance Co) has superior properties. The alloy has a high strength together with a good ductility which permits adequate workability. Also, both cobalt-chromium alloys show a passive behaviour in 6.0 wt% NaCl solution, whereas the basic type 18-8 austenitic stainless steel shows a fluctuating potential and is thus susceptible to pitting, making it unsuitable for surgical implants.     

Bioactive TiOB‐Coating on Titanium Alloy Implants Enhances Osseointegration in a Rat Model

The surface properties of titanium alloy implants for improved osseointegration in orthopaedic and dental surgery have been modified by many technologies. Hydroxyapatite coatings with a facultative integration of growth factors deposited by plasma spraying showed improved osseointegration. Our approach in order to enhance osseointegration was carried out by a surface modification method of titanium alloy implants called plasma chemical oxidation (PCO). PCO is an electrochemical procedure that converts the nm‐thin natural occurring titanium‐oxide layer on an implant to a 5 µm thick ceramic coating (TiOB‐surface). Bioactive TiOB‐surfaces have a porous microstructure and were loaded with calcium and phosphorous, while bioinert TiOB‐surfaces with less calcium and phosphorous loadings are smooth. A rat tibial model with bilateral placement of titanium alloy implants was employed to analyze the bone response to TiOB‐surfaces in vivo. 64 rats were randomly assigned to four groups of implants: (i) pure titanium alloy (control), ii) titanium alloy, type III anodization, (iii) bioinert TiOB‐surface, and (iv) bioactive TiOB‐surface. Mechanical fixation was evaluated by pull out tests at 3 and 8 weeks. The bioactive TiOB‐surface showed significantly increased shear strength at 8 weeks compared to all other groups.     

Mesenchymal stem cell adhesion and spreading on nanostructured biomaterials

Bone marrow-derived human mesenchymal stem cells were seeded in serum-free media onto ion beam-deposited nanostructured metalloceramic (Ti-Cr-N) films and plasma-nitrided titanium disks, which were left uncoated as well as precoated with fetal bovine serum. Precoating the disks with serum appears to stimulate cell spreading on both the titanium nitride and metalloceramic materials for as little as 1 hour incubation time. The implication is that both of these materials can adsorb serum proteins in amounts sufficient to influence cell adhesion and spreading for potentially improved in vivo response of orthopedic and dental implants. The materials in this study may prove to exhibit enhanced biological and mechanical properties when compared to conventional micron-scale implant materials such as titanium or cobalt-chrome alloys.     

Influence of acid-etching after grit-blasted on osseointegration of titanium dental implants: in vitro and in vivo studies

Rough implant surfaces have shown improved osseointegration rates. In a majority of dental implants, the microrough surfaces are obtained by grit blasting and/or acid-etching. The aim of this contribution was to evaluate the effects of acid-etching, after the grit-blasted treatment in titanium dental implants, on surface wettability, surface energy, osteoblast responses and its osseointegration behavior. Four surfaces were studied: as-machined, acid-etched, micro-rough by grit-blasting and the combination grit-blasted surface with acid-etched. The surfaces with increasing roughness show more osteoblastic adhered cells. This effect was most pronounced on samples blasted and blasted with acid-etching. The roughness obtained by grit-blasting is the main factor in comparison with the acid etching treatment in the biological response. These results were confirmed in vivo tests and histological analysis. The results demonstrated that the combination of the grit-blasted and acid-etched accelerated lightly bone regeneration at the different periods of implantation in comparison with the grit-blasted implants.     

Assessment of mechanical behaviour,microstructure and critical conditions of welded commercial purity titanium

An assessment of microstructure and mechanical properties of weldments in rolled and forged versions of commercially pure titanium has been undertaken. A comparison is also made between tungsten inert gas (TIG) and electron beam (EB) weldment properties.Fracture and fatigue behaviour of weldments have been investigated experimentally by fracture toughness and fatigue crack growth studies employing notched three point bend specimens. The implications of the data produced are expressed in a design philosophy which enables an estimate of critical defect size to be made based on either stable or unstable crack growth or plastic collapse. The conjoint action of fatigue and stable crack growth is also considered.     

低熔纯钛用体瓷的研制及其性能研究

采用硼硅酸盐玻璃体系制备低熔钛专用体瓷,研究了体瓷组成与热膨胀系数的关系,并采用XRD和细胞毒性实验分别研究了钛体瓷的晶相组成和生物相容性。结果表明,钛体瓷为不含晶体的均质玻璃体,其热膨胀系数随SiO2含量的增加而减小;通过对比两种配方的烧结温度与力学性能,最终确定体瓷配方和烧结工艺:自制钛体瓷的烧结温度为760℃,抗弯强度、断裂韧性和维氏硬度分别为(85±4.07)MPa、(1.44±0.04)MPa/m1/2和(3904±21.71)MPa/mm2,硬度稍高于天然牙釉质。XRD结果表明自制钛体瓷为不含晶体的均质玻璃体;细胞毒性为0级,对细胞无抑制作用,可望进一步应用于临床修复。     

A Study of Microstructures and Properties of High‐Carbon Si‐Cr Cast Steel Containing Rare Earth and Titanium

The microstructure, tensile and impact behaviour of high‐carbon Si‐Cr cast steel containing rare earth (RE) and titanium have been determined after austempering. The additions of RE and titanium refined the primary austenite grain size resulting in improving toughness. The addition of silicon handicapped the formation of carbide and carbide‐free bainitic ferrite and carbon enriched retained austenite could be obtained in the austempering structures of high‐carbon Si‐Cr cast steel, which had excellent mechanical properties and abrasion resistance. Moreover, the basic tendency of the mechanical properties of high‐carbon Si‐Cr cast steel influenced by the austempering temperature was that the hardness and tensile strength reduced and the impact toughness and fracture toughness increased with increasing temperature. The comprehensive properties were the best while austempering at 330^oC.     

Influence of the filler metal on the mechanical properties of Ti-6Al-4V electron beam weldments

The influence of various filler metals on the mechanical properties of 17 mm thick Ti-6Al-4V electron beam welded joints has been analysed. Autogeneous welded joints exhibit higher toughness when compared to the parent plate but this improvement was less marked than that observed in plasma arc welded joints. To achieve better toughness, without suffering unacceptable losses of strength, different morphologies of commercially pure titanium filler metals have been employed. Using 0.50 mm thick sheet as filler metal leaded to maximum toughness but as counterpart a significant decrease in strength was observed. To obtain high toughness while maintaining a high strength level 0.25 mm sheet and 1 mm diameter filler metals are recommended. Fractographic examination of the failed specimens helped to explain the fracture behaviour of the different welded joints.