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The changes in mechanical properties, hydrothermal degradation and cell adhesion were studied in 3Y-TZP under two different superficial modification patterns (uni- and multidirectional) with a surface roughness ranging from 16 to 603 nm. In this sense, mechanical properties (i.e. hardness, indentation fracture toughness and scratch) and accelerated tests in water steam were measured to evaluate the influence of the surface treatments on the superficially modified layer. Moreover, a detailed characterization through micro-Raman spectroscopy and X-Ray diffraction was performed. Finally, SaOS-2 osteoblasts were used for the evaluation of the cell adhesion behaviour on the surfaces. Overall, ground/polished specimens increased the mechanical properties and ageing resistance of mirror-like polished specimens, although resistance to degradation was maximum at intermediate conditions (Sa ˜ 40-180 nm). The studied surfaces allowed cell attachment, but promoted contact guidance (i.e. cell alignment) only on unidirectionally ground surfaces above Sa = 150 nm.

The market share of zirconia (ZrO2) dental implants is steadily increasing. This material comprises a polymorphous character with three temperature-dependent crystalline structures, namely monoclinic (m), tetragonal (t) and cubic (c) phases. Special attention is given to the tetragonal phase when maintained in a metastable state at room temperature. Metastable tetragonal grains allow for the beneficial phenomenon of Phase Transformation Toughening (PTT), resulting in a high fracture resistance, but may lead to an undesired surface transformation to the monoclinic phase in a humid environment (low-temperature degradation, LTD, often referred to as ‘ageing’). Today, the clinical safety of zirconia dental implants by means of long-term stability is being addressed by two international ISO standards. These standards impose different experimental setups concerning the dynamic fatigue resistance of the final product (ISO 14801) or the ageing behavior of a standardized sample (ISO 13356) separately. However, when evaluating zirconia dental implants pre-clinically, oral environmental conditions should be simulated to the extent possible by combining a hydrothermal treatment and dynamic fatigue. For failure analysis, phase transformation might be quantified by non-destructive techniques, such as X-Ray Diffraction (XRD) or Raman spectroscopy, whereas Scanning Electron Microscopy (SEM) of cross-sections or Focused Ion Beam (FIB) sections might be used for visualization of the monoclinic layer growth in depth. Finally, a minimum load should be defined for static loading to fracture. The purpose of this communication is to contribute to the current discussion on how to optimize the aforementioned standards in order to guarantee clinical safety for the patients.

The hydrolysis of lignocellulose is the first step in saccharide based bio-refining. The recovery of homogeneous acid catalysts imposes great challenges to the feasibility of conventional hydrolysis processes. Herein, we report a strategy to overcome these limitations by using stable sulfonated carbons as solid acid catalysts in a two-step process, composed of mechanocatalytic pretreatment and secondary hydrolysis in a semi-batch reactor. Without mechanocatalytic pre-treatment the hydrolysis of the insoluble substrate largely occurs through homogeneously catalyzed reactions. Ball-milling induced amorphization promotes a substantially higher substrate reactivity, because homogeneous hydrolysis occurs preferentially from less ordered structural domains in cellulose. In contrast, concerted ball-milling (CBM) of cellulose with the sulfonated carbon promotes a heterogeneously catalyzed hydrolysis to soluble oligosaccharides. By performing an in-depth physicochemical characterization of cellulose subjected to CBM treatment with different carbons, we reveal the crucial role of strong BrOnsted acid sites in facilitating mechanocatalytic depolymerization. Recyclability experiments confirmed that despite being subject to profound structural changes during repeated pre-treatment/semi-batch hydrolysis cycles, the sulfonated carbon retained its catalytic activity. The combination of mechanocatalytic pretreatment with strong solid acids and hydrolysis in the semi-batch reactor was successfully extrapolated for the first time to the hydrolysis of real lignocellulose to achieve quantitative yields in C-5 and high yields in C-6 derived products.

PURPOSE The aims of this study were to investigate mechanical properties and hydrothermal degradation behaviour of the cubic-containing translucent yttrium oxide stabilized tetragonal zirconia polycrystal (Y-TZP). MATERIALS AND METHODS Four groups of Y-TZP (T, ST, XT, and P), containing different amount of cubic crystal, were examined. Specimens were aged by autoclaving at 122℃ under 2 bar pressure for 8 h. Phase transformation was analyzed using X-ray diffraction (XRD) to measure phase transformation (t→m). Kruskal-Wallis test was used to determine the difference. Surface hardness, biaxial flexural strength, and fracture toughness in values among the experimental groups and verified with Wilcoxon matched pairs test for hardness values and Mann Whitney U for flexural strength and fracture toughness. RESULTS XRD analysis showed no monoclinic phase in XT and P after aging. Only Group T showed statistically significant decreases in hardness after aging. Hydrothermal aging showed a significant decrease in flexural strength and fracture toughness in group T and ST, while group XT and P showed no effect of aging on fractural strength and fracture toughness with P

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

OBJECTIVES: For the use of partially stabilized zirconia (PSZ) as high-translucent zirconia, the importance of cubic phase (c-ZrO2) is commonly emphasized without much attention for the remaining tetragonal phase (t-ZrO2). The aim is to understand whether the crystal structure and microstructure of t-ZrO2 have paramount influences on the properties of PSZ. METHODS: Two grades of 5mol% yttria-stabilized PSZ ceramics were prepared by different processing routes. A 5mol % yttria co-precipitated zirconia (T5Y) was compared with a 3 and 8mol% yttria-stabilized powder mixture grade with a bimodal grain size distribution (B5Y). The phase composition and lattice parameters were studied with x-ray diffraction (XRD) and Rietveld analysis. Mechanical properties were compared in terms of hardness, toughness and biaxial bending strength with Weibull analysis. Their translucency and aging stability were also characterized, and the microstructure before and after aging were followed by scanning electron microscopy (SEM). RESULTS: T5Y and B5Y having similar phase composition (about 40% t- and 60% c-ZrO2) showed the same basic properties (density, hardness and toughness), but the lattice parameters of t-ZrO2 and the concomitant microstructure were completely different. The t-ZrO2 phase in T5Y had a higher yttria content and a lower tetragonality (c/a) of 1.0126±0.0002, whereas the t-ZrO2 phase in B5Y was comparable to that in conventional 3Y-TZPs with a tetragonality of 1.0153±0.0002. Consequently, B5Y showed a lower strength with lower Weibull modulus, being less translucent and more aging susceptible as compared to T5Y. The translucency and aging susceptibility of B5Y were even comparable to those of conventional 3Y-TZP. SIGNIFICANCE: Not only the phase composition with high cubic phase content but also the lattice parameters and the yttria content in the remaining t-ZrO2 played a determinant role for PSZs to be used as 'high-translucent' zirconia. ispartof: DENTAL MATERIALS vol:36 issue:4 pages:491-500 ispartof: location:England status: published

© 2018 Elsevier Ltd The influence of 0.01–2 mol% Fe 2 O 3 powder addition on the microstructure, mechanical and optical properties, and hydrothermal stability of highly-translucent 3Y-TZP ceramics is assessed and compared with commercially available co-precipitated 0.18 mol% Fe 2 O 3 doped ZrO 2 powder-based ceramics. Only those ceramics with up to 0.1 mol% Fe 2 O 3 resulted in a proper shade for dental zirconia ceramics, with a typical composition of 87 vol% t-ZrO 2 and 13 vol% c-ZrO 2 . The amount of cubic phase increased at higher Fe 2 O 3 content. The hardness (∼13 GPa) and fracture toughness (∼3.6 MPa m 1/2 ) of the 0.01 mol% - 0.1 mol% Fe 2 O 3 doped 3Y-TZP was comparable, whereas the hardness decreased above 0.5 mol% Fe 2 O 3 and the fracture toughness decreased above 2 mol% Fe 2 O 3 . The hydrothermal ageing resistance slightly increased for Fe 2 O 3 concentrations up to 1 mol%, whereas the translucency slightly decreased with increasing Fe 2 O 3 content. ispartof: JOURNAL OF THE EUROPEAN CERAMIC SOCIETY vol:39 issue:2-3 pages:499-507 status: published

The effect of hydrothermal conditions on enzymatic hydrolysis lignin (EHL) degradation in water-isopropyl alcohol co-solvent and optimal conditions were investigated. The yields and reactivity toward formaldehyde of degraded enzymatic hydrolysis lignin (DEL) were determined. The optimal conditions of temperature, time, and ratio of solids to liquids were 250 °C, 60 min, and 1:10 (w/v), respectively. The EHL and DEL were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (1H NMR), thermal gravity (TG), and differential scanning calorimetry (DSC) analyses. The results revealed that the molecular weight and polydispersity of DEL were lower than that of EHL. Although the fundamental structure of lignin before and after hydrothermal degradation was retained, the ether (β-O-4, α-O-4, etc.) content decreased, while that of hydroxyl (phenolic and aliphatic) increased. The DTGmax and Tg values shifted from 334 and 117 °C to 304 and 105 °C, respectively.

Made available in DSpace on 2020-12-12T02:24:49Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-09-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ) Objectives: The aim of this study was to evaluate the effect of hydrothermal aging on the mechanical properties and translucency of dental zirconia with different levels of translucency. Methods: Three different types of dental yttria-stabilized zirconia were used: 3Y-TZP (ZrO2 - 3 mol.% Y2O3) of medium opacity (designated Z3OP), 3Y-TZP of medium translucency (Z3MT), and 5Y-PSZ (ZrO2 - 5 mol.% Y2O3) of high translucency (Z5HT). A total of 120 specimens were sintered (n = 40 specimens/group). The control group (sintered→polished→heat-treated) and the aged group (sintered→polished→heat-treated→hydrothermally degraded at 134 °C, 2 bar, 5h) were characterized by relative density, quantitative phase analysis by X-ray diffraction using the Rietveld method, microstructural analysis by scanning electron microscopy, surface roughness and translucency. All groups were submitted to a biaxial flexural strength test. Data analysis using Kruskal-Wallis, Nemenyi (p-value = 0.05), and Weibull statistics were used. Results: All sintered specimens presented full densification. After aging, an increase of the m-ZrO2 phase content was observed for the Z3OP group. On the other hand, Z3MT and Z5HT did not show any m-ZrO2 phase, indicating resistance to the hydrothermal degradation. Smaller grains were observed in the Z3MT group in relation to Z3OP group and the Z5HT group presented a bimodal grain distribution, where the largest grains were associated to cubic ZrO2. Z3OP exhibited a slight increase in roughness as a function of degradation, while the roughness remained statistically stable in the other groups. Translucency was little influenced by degradation, but considerably affected by increasing thickness. The Z5HT samples were the group with the highest translucency among the control groups. Z3OP exhibited the highest flexural strength, while being the most susceptible to hydrothermal degradation. The lowest values were presented by Z5HT in all groups, due to the high concentration of c-ZrO2 grains. Conclusion: Hydrothermal aging is less critical to the flexural strength of zirconia-based materials than the materials’ composition and microstructure. Z5HT zirconia showed the highest translucency, however the measured difference is not visually perceptible. Z5HT was considered the most resistant to hydrothermal degradation. Fluminense Federal University Faculty of Dentistry Institute of Health of Nova Friburgo, Dr. Silvio Henrique Braune St, 22 - Downtown Pontical Catholic University of Rio de Janeiro Department of Chemical and Materials Engineering PUC-Rio, Marques de São Vicente St 225, Gávea University of Toronto Faculty of Dentistry, 124 Edward St #539 State University of Rio de Janeiro Faculty of Technology, Presidente Dutra Highway, Km 298 São Paulo State University Faculty of Engineering of Guaratinguetá UNESP/FEG, Ariberto Pereira da Cunha Ave, 333 - Portal Das Colinas São Paulo State University Faculty of Engineering of Guaratinguetá UNESP/FEG, Ariberto Pereira da Cunha Ave, 333 - Portal Das Colinas CNPq: 308684/2013-3/311119/2017-4 FAPERJ: E-26-201.476/2014

Made available in DSpace on 2019-09-11T20:58:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2018 Abstract This study aimed to investigate slow crack growth (SCG) behavior of a zirconia ceramic after grinding and simulated aging with low-temperature degradation (LTD). Complementary analysis of hardness, surface topography, crystalline phase transformation, and roughness were also measured. Disc-shaped specimens (15 mm Ø × 1.2 mm thick, n = 42) of a full-contour Y-TZP ceramic (Zirlux FC, Amherst) were manufactured according to ISO:6872-2008, and then divided into: Ctrl – as-sintered condition; Ctrl LTD – as-sintered after aging in autoclave (134°C, 2 bar, 20 h); G – ground with coarse diamond bur (grit size 181 μm); G LTD – ground and aged. The SCG parameters were measured by a dynamic biaxial flexural test, which determines the tensile stress versus stress rate under four different rates: 100, 10, 1 and 0.1 MPa/s. LTD led to m-phase content increase, as well as grinding (m-phase content: Ctrl – 0%; G – 12.3%; G LTD – 59.9%; Ctrl LTD – 81%). Surface topography and roughness analyses showed that grinding created an irregular surface (increased roughness) and aging did not promote any relevant surface change. There was no statistical difference on surface hardness among different conditions. The control group presented the lowest strength values in all tested rates. Regarding SCG, ground conditions were less susceptible to SCG, delaying its occurrence. Aging (LTD) caused an increase in SCG susceptibility for the as-sintered condition (i.e. G < G LTD < Ctrl < Ctrl LTD). [Pereira, Gabriel Kalil Rocha] Faculdade Meriodional, Brazil Amaral, Marina] Universidade de Taubaté, Brazil Weitzel, Isabela Sandim Souza Leite] Universidade de Taubaté, Brazil Silvestri, Tais; Guilardi, Luis Felipe; Valandro, Luiz Felipe] Universidade Federal de Santa Maria, Brazil

[EN] Self-reinforced polymer composites (SRCs) are proposed as a suitable alternative for composite development, based in the combination of a polymeric matrix and a polymeric fibre made of the same polymer. SRCs based in polylactide (PLA) could be fully biodegradable and their valorisation routes could presumably be assimilated to those for neat PEA. In this sense, the aim of this study was to develop new self-reinforced PLA-based composites and ascertain their biodegradability. For this purpose, PLA-based SRCs were obtained through a thermo-compression procedure and their biodegradability corroborated under standard conditions (ISO 20200). Moreover, a deep study of the effect of the different factors involved in the biodegradation of the composites such as the temperature, the water and the compost medium was considered relevant to delimitate the long-term properties and valorisation routes for these materials. The macroscopic and microscopic appearance as well as the thermo-oxidative stability, the thermal properties and the molar mass were evaluated. Although degradation was perceived due to the effect of temperature, the synergistic combination of water and temperature and compost was found to play a key role in the biodegradation of these materials. Overall, these SRCs can be considered as promising candidates, since their end-of-life management options can be guaranteed under standardised composting conditions. (C) 2018 Elsevier Ltd. All rights reserved., The authors would like to thank the support of the European Regional Development Fund and the Spanish Ministry of Economy and Competitiveness, through the Research Projects ENE2014-53734-C2-1-R and UPOV13-3E-1947. The Spanish Ministry of Education, Culture and Sports is also thanked for the FPU grant for O. Gil-Castell (FPU13/01916). Generalitat Valenciana is recognised for the APOSTD14/041 program for J.D. Badia.

cited By 3; International audience; Objectives: The dental market moves towards high-translucency monolithic zirconia dental crowns, which are usually placed either with – or without – a thin glaze layer. The microstructural features and the mechanical performances of these materials are still controversial, as well as their susceptibility to aging. This paper aims at studying these aspects in the current generation of zirconia dental crowns showing different degrees of translucency. Methods: Four different commercial zirconia materials were investigated, including one standard ‘full-strength’ 3Y-TZP and three grades with improved translucency. The microstructural features (phase composition and assemblage, grain size) were carefully studied, as well as mechanical properties (biaxial bending strength and indentation toughness), translucency and aging behavior (in autoclave at 134 °C). Aging was conducted on crowns with and without glaze to better represent clinical uses. Results: Important differences are found in terms of microstructures among the materials in terms of cubic phase content and yttria in the tetragonal phase, leading to different optical, mechanical and aging resistance properties. We show that higher cubic phase content leads to better translucency and stability in water steam, but at the expense of strength and toughness. A compromise is always inevitable between translucency and aging resistance on one side and mechanical properties on the other side. Significance: - Even so called ‘high translucent’ zirconia ceramics tested in this work should be considered as medium translucency materials.- Aging occurs in standard state-of-the-art dental zirconia and glazing does not fully avoid this issue. However, aging did not compromise strength even after prolonged duration.- Aging is null in the ‘highly translucent’ zirconia grades but at the expense of strength, which is then comparable to glass-ceramics. © 2018 The Academy of Dental Materials

Made available in DSpace on 2019-09-12T16:53:37Z (GMT). No. of bitstreams: 0 Previous issue date: 2016 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) NUFFIC (Netherlands Organization for International Cooperation in Higher Education, The Netherlands) agency (Grants CAPES/NUFFIC) [056/14] The following study aimed to evaluate the effect of grinding and low-temperature aging on the fatigue limit of Y-TZP ceramics for frameworks and monolithic restorations. Disc specimens from each ceramic material, Lava Frame (3M ESPE) and Zirlux FC (Ivoclar Vivadent) were manufactured according to ISO:6872-2008 and assigned in accordance with two factors: (1) "surface treatment"-without treatment (as-sintered, Ctrl), grinding with coarse diamond bur (181 mu m; Grinding); and (2) "low-temperature aging (LTD)" - presence and absence. Grinding was performed using a contra-angle handpiece under constant water-cooling. LTD was simulated in an autoclave at 134 degrees C under 2-bar pressure for 20 h. Mean flexural fatigue limits (20,000 cycles) were determined under sinusoidal loading using stair case approach. For Lava ceramic, it was observed a statistical increase after grinding procedure and different behavior after LTD stimuli (Ctrl

The aim of this study is to establish a baseline for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) lifetime prediction in a marine environment, by means of mechanical and physico-chemical characterization of specimens immersed in continuously renewed and filtered natural seawater in the laboratory at different temperatures (4, 25 and 40°C). Samples were also aged at sea in Lorient harbour in order to compare laboratory and natural degradation mechanisms and kinetics. Due to its morphology, hydrolysis of PHBV in natural seawater is quite slow, and samples were observed to undergo preferentially an enzymatic surface degradation. Increasing the aging temperature in the laboratory promotes the water uptake and causes hydrolysis. As two degradation mechanisms occur in parallel, the choice of test conditions is critical, and the lifetime of PHBV in a marine environment is difficult to predict accurately.

International audience; Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-Ray Photoelectron Spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized pi-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade.