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OBJECTIVES: To evaluate two-body wear of three zirconia ceramics stabilized with 3, 4 and 5mol% yttria and to compare their wear behavior with that of a lithium-disilicate glass-ceramic. METHODS: Sixteen rectangular-shaped specimens made from three grades of zirconia ceramics and a lithium-disilicate glass-ceramic were polished and dynamically loaded in a chewing simulator (2kg vertical load, 2.1Hz) under water at 90°C for 1.2×106 cycles (about 7 days) in the ball-on-plate mode against steatite antagonists. Surface roughness was measured before and after wear testing. Wear tracks were scanned with a non-contact 3D profilometer and super-impositions were used to determine wear loss of the antagonists. Wear surfaces were imaged by SEM. XRD and micro-Raman spectroscopy were used to characterize phase transformation and stress status in the worn and unworn areas of the zirconia ceramics. RESULTS: Independent of fracture toughness, strength and aging-susceptibility, the three zirconia ceramics showed a similar and limited amount of wear (∼10μm in depth) and were more wear-resistant than the lithium-disilicate glass-ceramic (∼880μm in depth). Abrasive wear without obvious cracks was observed for all investigated zirconias, whereas the glass-ceramic with a lower fatigue threshold and high susceptibility to surface dissolution exhibited significant abrasion, fatigue and corrosion wear. All three zirconia ceramics yielded a lower antagonist wear than the glass-ceramic and no significant differences were found between the zirconia ceramics. SIGNIFICANCE: In the context of this study, high-translucent zirconia ceramics stabilized with a higher yttria content, recently introduced in the dental field, were as wear-resistant and antagonist-friendly as conventional high-strength zirconia and suitable for monolithic restorations. ispartof: DENTAL MATERIALS vol:35 issue:12 pages:1776-1790 ispartof: location:England status: published

International audience; 40 years ago, Garvie and his Australian co-workers reported that the stress induced transformation of metastable tetragonal zirconia grains to the monoclinic symmetry could give rise to a powerful toughening mechanism. Their results even led them to consider zirconia systems as analogues of certain steels. This seminal paper generated extraordinary excitement in the ceramic community and it is still the subject of extensive research. Transformation toughening is widely used in zirconia materials and results in an increase in strength and toughness when compared to non-transformable ceramics, but the implementation into strong, tough, and sufficiently stable materials has not been fully reached. Zirconia ceramics generally fail at low strains with a much larger scatter in the strength values than metals and require statistical approaches to failure. Here we describe in details the mechanical behavior laws of ceria-doped zirconia composites exhibiting a high degree of stress-induced transformation. They present, to some extent, mechanical behavior analogous to a metal, displaying, i) significant amount of transformation-induced plasticity without damage, ii) very high flaw

cited By 0; International audience; Twenty-year-old samples of (Mg,Y)-PSZ—Spinel composite were characterized to assess their microstructure and mechanical properties after such a long period of natural aging. The amount of the different phases was determined by XRD, whereas a detailed observation of the microstructural features was carried out by high-resolution SEM and FIB/SEM. Bending strength, hardness, and toughness were also measured. Translucency was quantified by measuring the contrast ratio (CR). After comparison of the results obtained in this study with those obtained 20 years ago, the studied material reveals a phase stability superior to that exhibited by conventional 3Y-TZP, good strength, and hardness and a remarkable toughness. The value of CR is comparable with those exhibited by the materials commonly used in dentistry. Thanks to the presence of spinel particles, grains are smaller than in conventional Mg-PSZ. In addition, we show here that grains can be further refined through spark plasma sntering. For all these reasons (Mg,Y)-PSZ-spinel composite could be proposed as valid alternative to 3Y-TZP for dental applications. © 2018 The American Ceramic Society

International audience; Hydrothermal ageing is one lifetime-limiting phenomenon of zirconia-based ceramics and composites for many applications, from biomedical implants to ferrules and watches. Predicting hydrothermal ageing at use-temperature implies a set of accelerated ageing experiments conducted under water vapour at several, high temperatures (usually between 100°C and 140°C). From these data, the activation energy of ageing can be determined, and thus ageing can be predicted at any temperature. However, obtaining precise extrapolations with this procedure requires the use of lower temperatures (70 or 80°C), leading to a rather long procedure (up to a few thousand hours), and should involve at least one specimen for each test temperature. This article presents a new procedure that allows the determination of all ageing parameters and the estimation of kinetics at use-temperatures with the use of a single specimen within a shorter time, accurate enough for fast screening of new materials.

International audience; Recent studies on zirconia-toughened alumina (ZTA) evidenced that in vivo aged implants display a much higher monoclinic zirconia content than expected from in vitro simulations by autoclaving. At the moment, there is no agreement on the source of this discrepancy: Some research groups ascribe it to the effect of mechanical impact shocks, which are generally not implemented in standard in vitro aging or hip walking simulators. Others invoke the effect of metal transfer, which should trigger an autocatalytic reaction in the body fluid environment, accelerating the kinetics of tetragonal-to-monoclinic transformation in vivo. Extrapolations of the aging kinetics from high (autoclave) to in vivo temperature are also often disputed. Last, Raman spectroscopy is by far the preferred method to quantify the amount of monoclinically transformed zirconia. There are, however, many sources of errors that may negatively affect Raman results, meaning that the final interpretation might be flawed. In this work, we applied Raman spectroscopy to determine the monoclinic content in as-received and in vitro aged ZTA hip joint implants, and in one long-term retrieval study. We calculated the monoclinic content with the most used equations in the literature and compared it with the results of X-ray diffraction obtained on a similar probe depth. Our results show, contrary to many previous studies, that the long-term surface stability of ZTA ceramics is preserved. This suggests that the Raman technique does not offer consistent and unique results for the analysis of surface degradation. Moreover, we discuss here that tetragonal-to-monoclinic transformation is also necessary to limit contact damage and wear stripe extension. Thus, the surface metastability of zirconia-containing ceramics may be a non-issue.

A very tough zirconia matrix is interesting to fabricate alumina-toughened zirconia (ATZ) and composites generally processed from 3Y-TZP do not exhibit very high toughness. The strategy of lowering the yttria content to increase toughness however is normally associated with an increased hydrothermal aging susceptibility. In this work, a 0.4 mol% La 2 O 3 doped 2Y-TZP matrix was investigated to realize a 20 wt.% alumina toughened zirconia composite with a substantially high aging resistance. The higher transformation toughening in the composite shifted the V-K I towards higher K I values, while preserving the slope of the curve, resulting in a threshold K I0 of 4.0 MPa m 1/2 and fracture toughness (K IC ) of 7.1 MPa m 1/2 . These composites can offer a better compromise between aging and crack resistance than traditional 3Y-TZPs and plain ATZ composites without La 2 O 3 doping.

The mechanisms by which calcium phosphate bone substitutes evolve and are resorbed in vivo are not yet fully known. In particular, the formation of intermediate phases during resorption and evolution of the mechanical properties may be of crucial interest for their clinical efficiency. The in vitro tests proposed here are the first steps toward understanding these phenomena. Microporous Dicalcium Phosphate Dihydrate (DCPD) samples were immersed in tris(hydroxymethyl)aminomethane (TRIS) and Phosphate Buffered Saline (PBS) solutions, with or without daily refresh of the medium, for time-points up to 14 days. Before and after immersion, samples were extensively characterised in terms of morphology, chemistry (XRD coupled with Rietveld analysis), microstructure (X-ray tomography, SEM observations) and local mechanical properties (instrumented micro-indentation). The composition of the immersion solutions was monitored in parallel (pH, elemental analysis). The results show the influence and importance of the experimental set-up and protocol on the formation of apatite and octacalcium phosphate concurrently to DCPD dissolution; moreover, strong inter-correlations between physico-chemistry, microstructure and mechanics are demonstrated. Statement of Significance Ideally, the resorption kinetics of biodegradable bone substitutes should be controlled to favor the healing processes of bone. Although biodegradable bone grafts are already used in surgeries, their resorption process is still partially unknown. The present work studies these resorption phenomena, their kinetics and mechanisms and their consequences on the properties of a calcium phosphate resorbable material. The original in vitro approach developed in this work couples for the first time physico-chemical, micro-structural and mechanical assessments. The dissolution of the CaP phase in body fluids and the reprecipitation of more stable phases are studied on a local scale, which has permitted to evidence and monitor the development of a gradient of properties between the surface and the core of the samples.

Ceramic materials are prone to slow crack growth, resulting in strength degradation over time. Although yttria-stabilized zirconia (Y-TZP) ceramics have higher crack resistance than other dental ceramics, their aging susceptibility threatens their long-term performance in aqueous environments such as the oral cavity. Unfortunately, increasing the aging resistance of Y-TZP ceramics normally reduces their crack resistance. Our recently conducted systematic study of doping 3Y-TZP with various trivalent cations revealed that lanthanum oxide (La2O3) and aluminum oxide (Al2O3) have the most potent effect to retard the aging kinetics of 3Y-TZP. In this study, the crack-propagation behavior of La2O3 and Al2O3 co-doped 3Y-TZP ceramics was investigated by double-torsion methods. The grain boundaries were examined using scanning transmission electron microscopy and energy-dispersive spectroscopy (STEM-EDS). Correlating these analytic data with hydrothermal aging studies using different doping systems, a strategy to strongly bind the segregated dopant cations with the oxygen vacancies at the zirconia-grain boundary was found to improve effectively the aging resistance of Y-TZP ceramics without affecting the resistance to crack propagation.

Ceramics are materials of choice for hip joint implants because of their excellent biocompatibility and mechanical properties. Wear of the bearing couple (femoral head and cup) remains one of the main concerns of hip implants. Although ceramics are known for their good tribological properties, shocks due to micro-separation, friction and hydrothermal ageing in physiological environment remain the three main sources of wear. It has been recently suggested that shock effects dominate but the three degradation mechanisms were so far simulated separately. We developed a procedure that combines sequences of shocks, hydrothermal ageing in an autoclave and friction on hip-walking simulator to investigate their combined effects on Zirconia Toughened Alumina (ZTA) implants. Our results confirm that shocks can be considered as the key phenomenon causing wear, and that their effect is independent of friction and hydrothermal degradation. The analysis of retrieved femoral heads reveals wear features comparable to the ones created experimentally by shocks. Standards (ASTM or ISO) could be improved by including shock tests, which are more relevant than wear tests currently performed on hip simulators at least for Ceramic-on- Ceramic couplings.

X-ray Computed Tomography (XCT) analysis was applied to identify and quantify typical defects in dense 3Y-TZP zirconia processed by the Lithography-based Ceramic Manufacturing (LCM) technique. XCT derived strengths were anticipated from the XCT data and compared to experimental measurement. A good agreement between XCT data, bending strength measurement and fractographic analysis demonstrates the suitability of X-ray tomography for both defects detection and predictive mechanical strength estimation. It allows also to rank the different defects related to LCM in terms of their criticality versus mechanical resistance.

cited By 2; International audience; Scaffolds for bone tissue engineering require a combination of bioactivity and bioresorption at the sample surface and high mechanical properties in the bulk. This work presents a novel calcium phosphate (CaP)/polycaprolactone (PCL) scaffold with graded composition and porosity fraction. The scaffold is made of (i) a dense hydroxyapatite (HA)/β-tricalcium phosphate (β-TCP) core, (ii) a macroporous HA/β-TCP transition layer and (iii) a macroporous PCL/(HA/β-TCP) external layer. The ceramic layers were fabricated by gel-casting whereas the outer composite layer was obtained by a solvent casting/particle leaching process. The microstructure, phase composition and biodegradation of the scaffolds were characterized. The gradient of porosity was clearly obtained whereas the gradation of phase composition was less pronounced. An in vitro dissolution test was performed by immersing the scaffolds in a TRIS solution. The results showed a dissolution phenomenon with possible differentiated mechanisms in the different layers, in relation with the targeted multi-functionality. © 2018 Elsevier B.V.

© 2018 Elsevier Ltd Slow crack growth (SCG) behavior of four zirconia-based composites reinforced with 40 vol% WC, TiC, NbC or TiCN were studied by means of double-torsion testing. Compared to monolithic zirconia, the composites had a higher resistance to fast fracture, i.e., higher fracture toughness. The extent of toughening depended on the reinforcement type, shifting the V-KI (crack velocity versus stress intensity factor) curve parallel to higher KI values. More importantly, these composites were less sensitive to SCG. Identical V-KI/KIC curves with steeper slopes compared to monolithic zirconia were observed for the investigated composites, independent on the reinforcement type. No rising R-curve was measured, at least in the crack-size domain investigated by SCG. Therefore, the higher SCG resistance of the composites was due to the intrinsic stress-assisted corrosion resistance of the covalent non-oxide secondary phase. ispartof: JOURNAL OF THE EUROPEAN CERAMIC SOCIETY vol:39 issue:2-3 pages:641-646 status: published

The efficiency of calcium phosphate (CaP) bone substitutes can be improved by tuning their resorption rate. The influence of both crystal orientation and ion doping on resorption is here investigated for beta-tricalcium phosphate (β-TCP). Non-doped and Mg-doped (1 and 6 mol%) sintered β-TCP samples were immersed in acidic solution (pH 4.4) to mimic the environmental conditions found underneath active osteoclasts. The surfaces of β-TCP samples were observed after acid-etching and compared to surfaces after osteoclastic resorption assays. β-TCP grains exhibited similar patterns with characteristic intra-crystalline pillars after acid-etching and after cell-mediated resorption. Electron BackScatter Diffraction analyses, coupled with Scanning Electron Microscopy, Inductively Coupled Plasma–Mass Spectrometry and X-Ray Diffraction, demonstrated the influence of both grain orientation and doping on the process and kinetics of resorption. Grains with c-axis nearly perpendicular to the surface were preferentially etched in non-doped β-TCP samples, whereas all grains with simple axis (a, b or c) nearly normal to the surface were etched in 6 mol% Mg-doped samples. In addition, both the dissolution rate and the percentage of etched surface were lower in Mg-doped specimens. Finally, the alignment direction of the intra-crystalline pillars was correlated with the preferential direction for dissolution. Statement of significance The present work focuses on the resorption behavior of calcium phosphate bioceramics. A simple and cost-effective alternative to osteoclast culture was implemented to identify which material features drive resorption. For the first time, it was demonstrated that crystal orientation, measured by Electron Backscatter Diffraction, is the discriminating factor between grains, which resorbed first, and grains, which resorbed slower. It also elucidated how resorption kinetics can be tuned by doping β-tricalcium phosphate with ions of interest. Doping with magnesium impacted lattice parameters. Therefore, the crystal orientations, which preferentially resorbed, changed, explaining the solubility decrease. These important findings pave the way for the design of optimized bone graft substitutes with tailored resorption kinetics.

cited By 0; This study aims to investigate the influence of different laser surface texturing parameters on Low-Temperature Degradation and mechanical properties of Yttria-tetragonal zirconia polycrystals (3Y-TZP), focused on biomedical applications. The roughness resulted from laser irradiation was characterized by Ra, Rt, Rsk and Rku parameters, as well by SEM analysis. Wettability tests were conducted as a guide to evaluate the ability of the textures to promote osseointegration. Eleven groups of samples were created, such as five according to the laser parameters used, three correspond to the thermal treatments performed and three as different standards. After laser irradiation, all 3Y-TZP samples became black having their whiteness recovered by thermal treatments, which was measured by color analysis. X-Ray photoelectron spectroscopy was used to evaluate chemical changes, presenting the formation of zirconium sub-oxides. These results were corroborated by wettability tests, which exhibited a decrease in surface energy after thermal treatments. Mechanical strength was evaluated by B3B tests, which reveals the potential of laser irradiation combined with thermal treatments for enhancing 3Y-TZP bending resistance and reliability. LTD was accessed by XRD and reveled laser irradiation as a promising approach able to improve the resistance of 3Y-TZP to this phenomenon. © 2019 Elsevier Ltd and Techna Group S.r.l.

The objective of this paper is to review the current knowledge on the development of nanostructured zirconia-based ceramics and composites suitable for application in dentistry. Isi Web of Science, Science Direct, Scientific.net databases, and Google were searched electronically for the period of 1980 to the present, matching the keywords “nano” with the keywords: “Zirconia, ZrO2, Y-TZP, and dental, dentistry”. A total of 74 papers were found, with the majority coming from Asia, indicating a more active scientific interest on the topic in this geographic area, followed by Europe, South America, and North America. The research shows, even though the scientific activity on nanostructured ceramics was intense in the last fifteen years, the development of fully dense zirconia-based nanoceramics is yet at an initial stage, most of all from the point of view of the clinical applications. It has been demonstrated that nanostructured ceramics can show improved properties because of the reduction of the grain size to the nanoscale. This is also true for zirconia-based nanoceramics, where some improvements in mechanical, optical, as well as resistance in low-temperature degradation have been observed. Potential applications of this class of material in the dental field are discussed, summarizing the results of the latest scientific research.

cited By 0; Resorbable ceramics used as porous bone substitutes are designed to favor bone in-growth and to be gradually replaced by natural tissues after in vivo resorption. However, a lack of experimental techniques to quantitatively monitor the evolution of their mechanical properties during resorption is noted. In this paper, we propose to use spherical instrumented indentation to follow-up the resorption of microporous resorbable ceramics at a local scale. Tests were performed at the core and at the surface of samples immersed for different durations in model fluids. Instrumented indentation was found to be an efficient technique to characterize and to follow-up the resorption of microporous ceramics, in excellent agreement with microstructural changes observed with X-ray diffraction and X-ray tomography. Instrumented indentation has the ability to capture the presence of gradients in the samples, enables the direct testing of wet samples and appears as a superior technique to compression tests mostly used in the literature. © 2019 Elsevier Ltd

High strength and translucency are generally not coincident in one restorative material and there is still a continuous development for a better balance between these two properties. Zirconia and lithium-disilicate glass-ceramics are currently the most popular alternatives for monolithic restorations. In this work, the mechanical properties and more important, the slow crack growth (SCG) resistance, which rules long-term durability, were thoroughly studied for three zirconia ceramics stabilized by 3, 4 and 5 mol% yttria in comparison to lithium-disilicate glass-ceramic. Translucency versus strength maps revealed that the more translucent zirconia compositions (i.e. with higher yttria contents) fill the gap between the standard 3 mol% yttria stabilized zirconia (3Y-TZP) and lithium-disilicate. Moreover, increasing yttria content did not always result in lower strength, as values for 3 mol% and 4 mol% yttria were the same. Independent on the yttria contents, all zirconia showed similar relative susceptibility to SCG under static and cyclic conditions and were significantly more SCG-resistant than lithium-disilicate glass ceramic. A concern with higher yttria contents (5 and 4 mol%) however could lie in the higher sensitivity to defects, resulting in a larger scatter in strength. STATEMENT OF SIGNIFICANCE: In addition to the common investigations on the generally reported strength, toughness and translucency, V-KI diagrams (crack velocity versus stress-intensity factor) from fast fracture to threshold for three newly developed zirconia were directly measured by double torsion methods under static and cyclic loading conditions. The crack-growth mechanisms were analyzed in depth. Results were compared with another popular dental ceramic, namely lithium-disilicate glass-ceramic, revealing the pros and cons of polycrystalline and glass-ceramics in terms of long-term durability. This is the first time that V-KI curves are compared for the major ceramic and glass-ceramic used for dental restorations. Strength versus translucency maps for different CAD/CAM dental restorative materials were described, showing the current indication range for zirconia ceramics. ispartof: ACTA BIOMATERIALIA vol:91 pages:24-34 ispartof: location:England status: published

Summary Gypsum microstructural evolution at elevated temperatures has been characterized in situ by environmental scanning electron microscopy and high-temperature X-ray tomography. As temperature increases, the observed changes in gypsum crystal morphology are related to the consequences of water loss that leads to crystal reorganization in order to minimize the specific surface. The influence of environmental scanning electron microscopy experimental conditions on the mechanisms observed is also discussed. High-temperature X-ray tomography gives quantitative information on porosity evolution with thermal loading. The results obtained are successfully correlated with macroscopic shrinkage measurements performed during dilatometry tests. Copyright © 2016 John Wiley & Sons, Ltd.

International audience; This paper aims at identifying the multiaxial compression behavior of highly porous ceramics used ascatalyst supports. For this purpose, instrumented spherical indentation tests are performed, togetherwith uniaxial and hydrostatic compression tests. A transition from a brittle to a damageable behaviorwith densification of the material is noted when increasing the triaxiality of the test. The collapse of largepores is shown as being responsible for the densification phenomenon, as confirmed by SEM andmercury intrusion porosimetry. A multiaxial damage criterion is proposed and identified thanks to anumerical finite element model.The results described in this paper coupled with a previous work (Staub et al., Oil and gas science andtechnology 2015, vol 70, n 3, 475e86) on the behavior of the same material under tension loading, allowfor the first time to define a multiaxial criterion both in tension and in compression for highly porousceramics. These materials are shown to present a typical behavior of dense ceramics in tension, whereasin compression, their behavior is close to that of porous rocks.

Incorporation of therapeutic ions into the structure of bioactive glasses for direct stimulation of cells is a very attractive approach for tissue engineering strategies. Lithium has recently been identified as a biologically active ion which can stimulate osteoblast cell activity. In this study, lithium-containing bioactive glasses (Li-BGs) where Li 2 O substitutes Na 2 O in different amounts (2.5, 5 and 10 wt.% Li 2 O) in 45S5 bioactive glass (BG) were produced and made into 3D scaffolds by the foam replica method. The structural changes that occur after heat treatment, the effect of lithium-content on the bioactivity of the glasses and their lithium ion release profiles were investigated. The results show that the novel Li-BG formulations exhibit the formation of an apatite-like layer on their surface after immersion in SBF for 1 day thus confirming their high surface reactivity, similar to undoped 45S5 BG. XRD results showed that the Li-doped BGs crystallize mainly to combeite (Na 2 Ca 2 Si 3 O 9 ) and silicorhenanite (SiO 4 (PO 4 ) 2 Ca 5 ) but also Li 6 P 6 O 18 and Li 3 PO 4 phases were detected. In terms of lithium ion release, the formulations at 2.5 wt.% and 5 wt.% Li 2 O content were the only ones to be within the therapeutic range (

Advanced bioceramics have played integral roles in treatment modalities for damaged or diseased human joints and osseous defects. This paper reviews the uses and properties of ceramics and ceramic coatings variously employed as articulation devices in hip, knee, shoulder, and other joints, either as self-mated surfaces, or against polyethylene (both conventional and highly cross-linked versions), or for osseous- fixation as arthrodesis devices, bone scaffolds, and substitutes in the spine or extremities. The modern uses of oxide and non-oxide materials in these applications will be discussed, followed by an assessment and comparison of their mechanical and physicochemical properties. Recent developments in new bioceramic materials and composites along with advanced processing and testing methods are presented. Advanced bioceramics and coatings are expected to have increasing use in orthopaedics because of their unique combination and range of properties including strength and toughness, hardness and wear resistance, biocompatibility, bacteriostasis, and osseointegration.

Tetragonal Zirconia Polycrystals (TZP) is attractive for structural biomedical applications because of their excellent mechanical properties at room-temperature, which include high strength, fracture toughness and wear resistance. In this work, zirconia stabilized with Y or Yb or Yb+Nd, all containing 0.5 vol.% Al2O3, were prepared by hot-pressing (HP) at 50–60 MPa and sintered at 1300–1350 °C for 1 h. Microstructural features, phase composition and mechanical properties were investigated. The strength was measured by 4-point bending (4P-B), piston-on-three-balls (P-3B) and three-balls-on-three-balls (3B-3B) biaxial methods. Toughness was determined by indentation strength in bending (ISB). Vickers hardness (Hv) and the Young modulus (E) were also estimated. Preliminary aging behaviour (LTD) was also here considered. Measured biaxial strength was significantly higher (until 1.83 times) than the uniaxial one because of the tetragonal to monoclinic (t-m) zirconia phase transformation which is strongly influenced by the loading configuration. The variation of the strength with the testing method is attributed to the compressive stresses generated by the phase transformation which is particularly favoured under P-3B tests and also to the calculation of the stresses from elastic theories. LTD preliminary tests showed excellent aging resistance of 3Yb-0.5A ceramics.

The aging behavior of 3-mol%-yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics sintered in air and in reducing conditions was investigated at 140{\deg}C in water vapor. It was observed by X-ray diffraction (XRD) that 3Y-TZP samples sintered in reducing conditions exhibited significantly higher tetragonal-to-monoclinic transformation than samples with similar density and average grain size values but obtained by sintering in air. This fact is explained by the increase of the oxygen vacancy concentration and by the presence at the grain boundary region of a new aggregate phase formed because of the exolution of Fe2+ ions observed by X-ray photoelectron spectroscopy., Comment: 10 pages, 3 figures

International audience; Orthopaedic-implant-related infections are challenging for clinicians: despite progresses in surgical procedures, the mortality rate of patients experiencing periprosthetic joint infections still ranges from 10 to 18%. Generally, infection starts when planktonic bacteria arising from surgery escape immunological surveillance adhering onto implant surface. Bacterial adhesion depends mainly on material’s intrinsic surface features depending on its chemical and physical properties. This study compares materials used for bearings of total hip arthroplasty, advanced ceramics (alumina and zirconia-platelet toughened alumina composites), metals (cobalt–chromium–molybdenum alloy) and polymers (highly cross-linked polyethylene), in terms of wettability and protein adsorption. Materials were infected with Staphylococcus aureus and Staphylococcus epidermidis biofilm for 24 or 48 h. Bacterial adhesion properties were evaluated by means of biofilm viability, morphology, and thickness, in a worst-case surface roughness condition. Thanks to selective protein adsorption, bioceramics reduced bacterial adhesion and subsequent biofilm formation more effectively in comparison with metal and polymer surfaces.

International audience; Literature is quite abundant concerning the resorption of calcium phosphates. However, articles on in vitro acellular dissolution tests are scarcer, although these immersion experiments are often considered a first step in establishing a predictive dissolution test and understanding the resorption mechanisms. Also, the comparison of results obtained after immersion in model fluids reveals large discrepancies.The first part of this paper is a literature review focused on in vitro aging of apatite, dicalcium phosphate dihydrate (DCPD) and beta tricalcium phosphate (β-TCP). In the second part, experimental findings obtained by immersing DCPD and β-TCP samples in TRIS and PBS solutions for different times demonstrate the influence of the immersion conditions and possible artefacts induced by the experimental protocols. Suggestions are provided to improve the design of in vitro experiments. In addition, the interest to follow-up at the same time and at a local scale physico-chemical, microstructural and mechanical properties is discussed.

International audience; Ti40Zr10Cu36Pd14 Bulk Metallic Glass (BMG) appears very attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements such as Ni, Al or Be and its good mechanical properties. For the first time, a complete and exhaustive characterization of a unique batch of this glassy alloy was performed, together with ISO standard mechanical tests on machined implant-abutment assemblies. The results were compared to the benchmark Ti-6Al-4V ELI (Extra-Low-Interstitial) to assess its potential in dental implantology. The thermal stability, corrosion and sterilization resistance, cytocompatibility and mechanical properties were measured on samples with a simple geometry, but also on implant-abutment assemblies' prototypes. Results show that the glassy alloy exhibits a quite high thermal stability, with a temperature range of 38 degrees C between the glass transition and crystallization, a compressive strength of 2 GPa, a certain plastic deformation (0.7%), a hardness of 5.5 GPa and a toughness of 56 MPa.m. Moreover, the alloy shows a relatively lower Young's modulus (96 GPa) than the Ti-6Al-4V alloy (110-115 GPa), which is beneficial to limit bone stress shielding. The BMG shows a satisfactory cytocompatibility, a high resistance to sterilization and a good corrosion resistance (corrosion potential of -0.07 V/SCE and corrosion current density of 6.0 nA/cm(2)), which may ensure its use as a biomaterial. Tests on dental implants reveal a load to failure 1.5-times higher than that of Ti-6Al-4V and a comparable fatigue limit. Moreover, implants could be machined and sandblasted by methods usually conducted for titanium implants, without significant degradation of their amorphous nature. All these properties place this metallic glass among a promising class of materials for mechanically-challenging applications such as dental implants.

The isothermal tetragonal-to-monoclinic transformation of 3Y-TZP ceramics sintered at two different temperatures (1450{\deg}C and 1550{\deg}C) and duration (2 and 5 h) is investigated at 134{\deg}C in steam. Particular attention is paid to the presence of a cubic phase and its effect on isothermal aging. Sintering at 1550{\deg}C can result in a significant amount of large cubic grains in the specimens, that have a detrimental impact on aging resistance, especially for the first stage of the aging process. Cubic grains appear to be enriched in yttrium, which in turn leads to a depletion of yttrium in the neighboring tetragonal grains. These grains will act as nucleation sites for tetragonal-to-monoclinic transformation. Even for specimens sintered at lower temperature, i.e. 1450{\deg}C, the presence of a cubic phase is expected from the phase diagram, leading to a significant effect on aging sensitivity., Comment: 11 pages, 7 figures

cited By 1; International audience; Conventional composites often do not represent true synergy of their constituent materials. This is particularly evident in biomaterial applications where devices must interact with cells, resist cyclic loads and biodegrade safely. Here we propose a new hybrid system, with co-networks of organic and inorganic components, resulting in unprecedented mechanical properties, including "bouncy" elasticity and intrinsic ability to self-heal autonomously. They are also developed as new 'inks' that can be directly 3D printed. A hybrid is different from a nanocomposite because the components are indistinguishable from each other at the nanoscale and above. The properties are generated by a novel methodology that combines in situ cationic ring-opening polymerisation with sol-gel, creating silica/poly(tetrahydrofuran)/poly(ϵ-caprolactone) hybrids with molecular scale interactions and covalent links. Cartilage is notoriously difficult to repair and synthetic biomaterials have yet to mimic it closely. We show that 3D printed hybrid scaffolds with pore channels of ∼200 μm mimic the compressive behaviour of cartilage and provoke chondrocytes to produce markers integral to articular cartilage-like matrix. The synthesis method can be applied to different organic sources, leading to a new class of hybrid materials.

Objectives The purpose of this work is a proof of concept to introduce a new quantitative 3D-analysis of dental erosion obtained by focused ion beam (FIB) tomography associated with silver nitrate penetration into porosities in etched enamel. Methods One sample selected was sound enamel after removal of the aprismatic surface. The other was studied after applying an additional attack with orthophosphoric acid. Both surfaces were infiltrated with silver nitrate via immersion. After dehydration, samples were observed in a dual column FIB/SEM station. Serial FIB sectioning was conducted with a current of 3 nA at 30 keV and an increment step of 20 nm for the healthy enamel and of 40 nm for the etched one. 3D analysis was performed with Fiji software and BoneJ plugin and several parameters were obtained to characterize the tissue: non-mineralized phase content (NMP), connected porosity fraction (CPF) and degree of anisotropy (DA) of the NMP. Results Healthy enamel showed an NMP content of 0.5 vol.%, with a bimodal distribution of non-mineralized regions, inside the prisms and between the prisms. No silver penetration was noticed in the healthy enamel, demonstrating the absence of open porosity. In contrast, silver nitrate penetration after acidic exposure was observed, up to a depth of 12 μm, which allowed the calculation of an interconnected porosity volume fraction (CPF) of 3.1 vol.%, mostly between the prisms. Values for DA of 0.56 for sound enamel and 0.81 for acid-etched surface were determined, highlighting a higher degree of anisotropy in the latter. Significance Quantitative analysis of FIB tomography using NMP, CPF and DA should contribute to a better understanding and follow up of dental erosion, correlation between erosion and attrition or abrasion process, and the ability to develop enamel remineralization procedures.

Oxide ceramics are sensitive to slow crack growth because adsorption of water can take place at the crack tip, leading to a strong decrease of the surface energy in humid (or air) conditions. This is a major drawback concerning demanding, long-term applications such as orthopaedic implants. Here we show that a specific nanostructuration of ceramic oxides can lead to a crack resistance never reached before, similar to that of covalent ceramics., Comment: 9 pages, 5 figures

There is a growing interest in the development of composites with complex structures designed to generate enhanced mechanical properties. The challenge is how to implement these structures in practical materials with the required degree of control. Here we show how freeze casting of ceramic preforms combined with metal infiltration can be used to fabricate Al 2 O 3 /Al-4wt% Mg micro-laminated composites. By manipulating the solid content of the suspension and the morphology of the ceramic particles (from platelets to round particles) it is possible to access a range of structures with layer thickness varying between 1 and 30 μm and metallic contents between 66 and 86 vol%. The mechanical response of the materials is characterized by combining bending tests with observation of crack propagation in two and three dimensions using different imaging techniques. These composites are able to combine high strength and toughness. They exhibit a rising R-curve behaviour although different structures generate different toughening mechanisms. Composites fabricated with Al 2 O 3 particles exhibit the highest fracture resistance approaching 60 MPa m 1/2 , while laminates prepared from Al 2 O 3 platelets exhibit higher strengths (above 700 MPa) while retaining fracture resistance up to ∼40 MPa m 1/2 . The results provide new insights on the effect of structure on the mechanical properties in metal-ceramic composites as well as on the design of appropriate testing procedures.

Recently, several episodes of fracture of zirconia ceramic femoral heads of total hip prostheses have alarmed the medical and scientific community regarding aging problems in zirconia prostheses. Such fractures cause immediate local tissue reactions, which require urgent medical intervention to prevent further complications. Thus, an upper limit of yttria-stabilized zirconia (Y-TZP) concentration in alumina/Y-TZP composites was found to avoid future aging problems. This limit coincides with the percolation threshold measured by infrared (IR) reflectance in a series of alumina/Y-TZP composites., The authors acknowledge the EU for the financial support under the GROWTH2000, project reference GRD2‐2000‐25039.

Silicon carbide (SiC) is being used increasingly as a room temperature structural material in environments where moisture cannot always be excluded. Unfortunately, there have been almost no reports on slow crack growth (SCG) in SiC at room temperature. To address this gap, SCG in SiC was studied using constant stress rate and double torsion tests in water. SiC based materials were produced with a wide range of grain boundary chemistries and microstructures, which may affect their slow crack growth behaviour. To clarify the role of chemistry and microstructure respectively, solid state (SS) sintering with carbon and boron along with liquid phase (LP) sintering using oxides additives were used to produce materials with fine and coarse grains. The LP-SiC was three times more sensitive to SCG than SS-SiC materials. Moreover, the larger grained material with a higher toughness was less sensitive to SCG than the materials with fine grains.

Poly(lactic acid) is nowadays among the most used bioabsorbable materials for medical devices. To promote bone growth on the material surface and increase the degradation rate of the polymer, research is currently focused on organic- inorganic composites by adding a bioactive mineral to the polymer matrix. The purpose of this study was to investigate the ability of a poly(L,DL-lactide)-BioglassV R (P(L,DL)LA-Bioglass V R 45S5) composite to be used as a bone fixation device. In vitro cell viability testing of P(L,DL)LA based composites containing different amounts of Bioglass V R 45S5 particles was investi- gated. According to the degradation rate of the P(L,DL)LA matrix and the cytocompatibility experiments, the composite with 30 wt % of BioglassV R particles seemed to be the best candidate for further investigation. To study its behavior after immersion in simulated physiological conditions, the degradation of the composite was analyzed by measuring its weight loss and mechanical properties and by proceeding with X-ray tomogra- phy. We demonstrated that the presence of the bioactive glass significantly accelerated the in vitro degradation of the poly- mer. A preliminary in vivo investigation on rabbits shows that the addition of 30 wt % of Bioglass V R in the P(L,DL)LA matrix seems to trigger bone osseointegration especially during the first month of implantation. This composite has thus strong potential interest for health applications. V C

We demonstrate in this paper that atomic force microscopy can be successfully used to gain further insights into the understanding of transformation toughening in ceria stabilized zirconia. Transformation was induced by stresses accumulated in the region surrounding propagating cracks in double torsion samples. The resolution provided by AFM at the surface of the samples made it possible to observe the formation of self accommodated martensite pairs in the near crack areas. The potential for transformation is found to decrease with increasing alloying addition, and is totally suppressed for 16 mol.% CeO2-TZP samples. A statistical analysis of the martensite pair orientation is performed, and the relationship with the applied stress and strain fields is discussed. The contribution to transformation toughening by transformation-induced plasticity occurring in the formation of martensitic variant pairs with small net shear is demonstrated. The influence of alloying addition content on the potential for transformation toughening and fracture toughness values is finally discussed., 21 pages, 10 figures

Zirconia-based materials have been used in orthopaedics since the 1980s, with large success, mainly thanks to transformation toughening. On the other hand, their main drawback is their potential sensitivity to hydrothermal ageing, i.e. tetragonal to monoclinic phase transformation on their surface in the presence of water. Hydrothermal ageing may result in roughness increase and microcracking of the surface. In this article the hydrothermal ageing behaviour of three medical-grade zirconia-based materials is assessed at high temperature and extrapolated to room or body temperature. The degradation is also characterized by FIB/SEM nano-tomography to better assess sub-surface evolutions. In both zirconia and alumina-toughened zirconia (ATZ), ageing results in the presence of a homogenous transformed layer of constant thickness whose growth rate is about 8 times slower in ATZ than in zirconia. Microcracking occurs in the entire transformed layer in zirconia, but was much less relevant in ATZ. Zirconia-toughened alumina (ZTA) is much less prone to ageing. In ZTA ageing results in a thin transformed layer in which the monoclinic fraction decreases with depth. No microcracking was observed in ZTA. Statement of Significance This article details the microstructural evolution of the surface of three zirconia-based ceramics when exposed to water (hydrothermal ageing), and establishes a time-temperature equivalences of these evolutions. It shows that different zirconia-alumina composites do not degrade the same way: zirconia and alumina-toughened zirconia present a homogeneous degraded zone of constant thickness, whereas zirconia-toughened-alumina presents a gradient of transformation. These new findings will help understanding better the hydrothermal degradation of zirconia based materials, and in particular will facilitate a better prediction of the durability of zirconia-based devices such as orthopaedic implants and dental devices (implants, crowns, abutments…).

International audience; During the sintering process of ceramic pieces, temperature gradients may arise inside the piece if the thermal cycle is too fast with regards to the size of the ceramic body. Too large temperature gradients may lead to density gradients, thus to strain gradients which may result in defects or in the fracture of the pieces. This article presents both an experimental setup and the first steps towards a numerical method to evaluate these thermal gradients and their evolutions during sintering, in the case of large zirconia, alumina and zirconia-toughened alumina balls. Finally it discusses the advantages of Rate Controlled Sintering thermal cycles in terms of diminishing the temperature gradients during densification.

Ceramics for restorative dentistry should satisfy some major requirements: biocompatibility, esthetic properties, and mechanical performance, to ensure proper reliability and lifetime to the dental devices. By keeping in mind such requirements and related applications, this chapter aims to provide some guidelines for the design and development of innovative ceramics for the next generation of dental products and to indicate the direction for future developments. Three main strategies are illustrated here concerning the design of new dental restorative materials. The first strategy focuses on strong, tough, and stable zirconia-based ceramics, needed for dental parts and implants subjected to the highest stresses. The second is the biomimetic approach, in which the design of dental ceramics is inspired by the human tooth architecture and functions. Functionally graded ceramics as well as mineralized tissue-based hierarchical structures have recently been designed and developed to this aim. The third ambitious strategy relates to tissue engineering in dentistry, showing the most recent advances for regenerating the whole-tooth complex in a biological manner.

International audience; no abstract

Zirconia-based composites were developed through an innovative processing route able to tune compositional and microstructural features very precisely. Fully-dense ceria-stabilized zirconia ceramics (84 vol% Ce-TZP) containing equiaxed alumina (8 vol%Al 2 O 3 ) and elongated strontium hexa-aluminate (8 vol% SrAl 12 O 19 ) second phases were obtained by conventional sintering. This work deals with the effect of the zirconia stabilization degree (CeO 2 in the range 10.0–11.5 mol%) on the transformability and mechanical properties of Ce-TZP-Al 2 O 3 -SrAl 12 O 19 materials. Vickers hardness, biaxial flexural strength and Single-edge V-notched beam tests revealed a strong influence of ceria content on the mechanical properties. Composites with 11.0 mol% CeO 2 or above exhibited the classical behaviour of brittle ceramics, with no apparent plasticity and very low strain to failure. On the contrary, composites with 10.5 mol% CeO 2 or less showed large transformation-induced plasticity and almost no dispersion in strength data. Materials with 10.5 mol% of ceria showed the highest values in terms of biaxial bending strength (up to 1.1 GPa) and fracture toughness (>10 MPa√m). In these ceramics, as zirconia transformation precedes failure, the Weibull modulus was exceptionally high and reached a value of 60, which is in the range typically reported for metals. The results achieved demonstrate the high potential of using these new strong, tough and stable zirconia-based composites in structural biomedical applications. Statement of Significance Yttria-stabilized (Y-TZP) zirconia ceramics are increasingly used for developing metal-free restorations and dental implants. Despite their success related to their excellent mechanical resistance, Y-TZP can undergo Low Temperature Degradation which could be responsible for restoration damage or even worst the failure of the implant. Current research is focusing on strategies to improve the LTD resistance of Y-TZP or to develop alternative composites with better stability in vivo . In this work the mechanical characterization of a new type of very-stable zirconia-based composites is presented. These materials are composed of ceria-stabilized zirconia (84 vol%Ce-TZP) containing two second phases (α-alumina and strontium hexa-aluminate) and exhibit exceptional strength, toughness and ductility, which may allow the processing of dental implants with a perfect reliability and longer lifetime.

Bone fracture is a major health issue worldwide and consequently there have been extensive investigations into the fracture behavior of human cortical bone. However, the fracture properties of human cortical bone under fall-like loading conditions remains poorly documented. Further, most published research has been performed on femoral diaphyseal bone, whereas it is known that the femoral neck and the radius are the most vulnerable sites to fracture. Hence, the aim of this study is to provide information on human cortical bone fracture behavior by comparing different anatomical sites including the radius and the femoral neck acquired from 32 elderly subjects (50 – 98 y.o.). In order to investigate the intrinsic fracture behavior of human cortical bone, toughness experiments were performed at two different strain rates: standard quasi-static conditions, and a higher strain rate representative of a fall from a standing position. The tests were performed on paired femoral neck, femoral, tibial and radius diaphyseal samples. Linear elastic fracture toughness and the non-linear J-integral method were used to take into account both the elastic and non-elastic behavior of cortical bone. Under quasi-static conditions, the radius presents a significantly higher toughness than the other sites. At the higher strain rate, all sites showed a significantly lower toughness. Also, at the high strain rate, there is no significant difference in fracture properties between the four anatomical sites. These results suggest that regardless of the anatomical site (femur, femoral neck, tibia and radius), the bone has the same fracture properties under fall loading conditions. This should be considered in biomechanical models under fall-like loading conditions.

International audience; The surface morphologies and microstructures of Zirconia Toughened Alumina (ZTA)femoral heads were analyzed followingin vitrotests aiming to simulatein vivodegradation. Threephenomena potentially leading to degradation were investigated: shocks, friction and hydrothermalageing. Shocks due to micro-separation created the main damage with the formation of wear stripeson the femoral head surfaces. Atomic Force Microscopy (AFM) images suggested the release of weardebris of various shapes and sizes through inter- and intra-granular cracks; some debris may have asize lower than 100 nm. A decrease in hardness and Young’s modulus was measured within the wearstripes by nanoindentation technique and was attributed to the presence of surface and sub-surfacemicro-cracks. Such micro-cracks mechanically triggered the zirconia phase transformation in thoseworn areas, which in return presumably reduced further crack propagation. In comparison withshocks, friction caused little wear degradation as observed from AFM images by scarce pullout ofgrains. The long-term resistance of the ZTA composite material against hydrothermal ageing isconfirmed by the present observations

Bioinert zirconia and alumina ceramic devices are widely used, both in orthopaedics and in dentistry. In order to improve their bonding with bone tissues or dental resin cements, their surfaces are often roughened at different scales. In this work, we have investigated the effects of the same sandblasting treatment on alumina, zirconia and a zirconia-toughened alumina, focusing on their mechanical performance and the interplay between surface defects and residual stresses. Additionally, we explored the impact of the treatment on the hydrothermal aging of the two zirconia-containing materials. Residual stresses generated during sandblasting were always predominant over surface defects but their effect varied with the material: while they had a weakening effect on alumina, they reinforced both zirconia-containing materials. Finally, we found that the monoclinic grains at the surface of sandblasted zirconia recrystallized into tetragonal nanograins after annealing and this led to an increased resistance to aging.

Yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) with different microstructures were elaborated. The isothermal tetragonal to monoclinic transformation was investigated at 134 {\deg}C in steam by X-ray diffraction, Atomic Force Microscopy (AFM) and optical interferometry. The aging kinetics were analyzed in terms of nucleation and growth, using the Mehl-Avrami-Johnson (MAJ) formalism. Numerical simulation of the aging of zirconia surfaces was also conducted, and the results were used to better fit the aging kinetics. The simulation shows that the exponent of the MAJ laws is controlled not only by the nucleation and growth mechanisms, but also - and mainly - by their respective kinetic parameters. Measurements of nucleation and growth rates at the surface, at the beginning of aging, and the use of numerical simulation allow the accurate prediction of aging kinetics., Comment: 20 pages, 9 figures

The development of long-lasting zirconia-based ceramics for implants, which are not prone to hydrothermal aging, is not satisfactorily solved. Therefore, this study is conceived as an overall evaluation screening of novel ceria-stabilized zirconia–alumina–aluminate composite ceramics (ZA8Sr8-Ce11) with different surface topographies for use in clinical applications. Ceria-stabilized zirconia is chosen as the matrix for the composite material, due to its lower susceptibility to aging than yttria-stabilized zirconia (3Y-TZP). This assessment is carried out on three preclinical investigation levels, indicating an overall biocompatibility of ceria-stabilized zirconia-based ceramics, both in vitro and in vivo. Long-term attachment and mineralized extracellular matrix (ECM) deposition of primary osteoblasts are the most distinct on porous ZA8Sr8-Ce11p surfaces, while ECM attachment on 3Y-TZP and ZA8Sr8-Ce11 with compact surface texture is poor. In this regard, the animal study confirms the porous ZA8Sr8-Ce11p to be the most favorable material, showing the highest bone-to-implant contact values and implant stability post implantation in comparison with control groups. Moreover, the microbiological evaluation reveals no favoritism of biofilm formation on the porous ZA8Sr8-Ce11p when compared to a smooth control surface. Hence, together with the in vitro in vivo assessment analogy, the promising clinical potential of this novel ZA8Sr8-Ce11 as an implant material is demonstrated.

Porous extrudates consisting of a packing of model spherical alumina particles with different median diameters (1.7 μm and 19 μm) were prepared. Peptized boehmite and aluminophosphate binders were used in order to ensure the cohesion of the materials. Combined effect of the multiscale packing of porous alumina particles contributed to generate supports with low binder content and good mechanical strength. The resulted microstructure is very attractive for porous materials such as catalyst supports and adsorbents and can be easily controlled by selecting relevant filler particles.