Mechanical properties of 3D-printed and milled composite resins for definitive restorations: An in vitro comparison of initial strength and fatigue behavior.

OBJECTIVE: To evaluate the flexural strength and fatigue behavior of a novel 3D-printed composite resin for definitive restorations. MATERIALS AND METHODS: Fifty disc-shaped specimens were manufactured from each of a nanohybrid composite resin (NHC), polymer-infiltrated ceramic network (PICN), and 3D-printed composite resin (3D) with CAD-CAM technology. Biaxial flexural strength (σin ) (n = 30 per group) and biaxial flexural fatigue strength (σff ) (n = 20 per group) were measured using piston-on-three-balls method, employing a staircase approach of 105 cycles. Weibull statistics, relative-strength degradation calculations, and fractography were performed. The results were analyzed with 1-way ANOVA and Games-Howell post hoc test (α = 0.05). RESULTS: Significant differences in σin and σff among the groups (p < 0.001) were detected. The NHC group provided the highest mean ± standard deviation σin and σff (237.3 ± 31.6 MPa and 141.3 ± 3.8 MPa), followed by the PICN (140.3 ± 12.9 MPa and 73.5 ± 9.9 MPa) and the 3D (83.6 ± 18.5 MPa and 37.4 ± 23.8 MPa) groups. The 3D group exhibited significantly lower Weibull modulus (m = 4.7) and up to 15% higher relative strength degradation with areas of nonhomogeneous microstructure as possible fracture origins. CONCLUSIONS: The 3D-printed composite resin exhibited the lowest mechanical properties, where areas of nonhomogeneous microstructure developed during the mixing procedure served as potential fracture origins. CLINICAL SIGNIFICANCE: The clinical indications of the investigated novel 3D-printed composite resin should be limited to long-term provisional restorations. A cautious procedure for mixing the components is crucial before the 3D-printing process, since nonhomogeneous areas developed during the mixing could act as fracture origins.

Effect of airborne particle abrasion and regeneration firing on the strength of 3D-printed 3Y and 5Y zirconia ceramics.

OBJECTIVES: This study aimed to assess the effect of airborne particle abrasion (APA) and regeneration firing (RF) on the subsurface damage and strength distribution of 3D-printed 3Y-TZP and 5Y-PSZ zirconia parts for dental applications. METHODS: Disc-shaped specimens were prepared using vat photopolymerization (VPP) technology from 3Y and 5Y zirconia ceramics, followed by thermal debinding and sintering. APA treatment with 50 µm Al2O3 particles and RF at 1000 °C for 15 min were applied. Microstructural analysis was conducted using FIB-SEM, and XRD analysis determined crystalline phase content. Biaxial flexural strength was measured using the ball on three balls method and analyzed with Weibull statistics. ANOVA and Tukey HSD test were employed to compare strength differences between groups. RESULTS: APA treatment increased the flexural strength of the 3Y specimens but decreased it for the 5Y specimens. RF treatment reversed the effect, restoring the strength to as-sintered levels for both materials. APA-treated 3Y specimens exhibited characteristic strength values above 1400 MPa, attributed to phase-transformation toughening. As sintered 5Y specimens showed strength values above 600 MPa. APA treatment increased the Weibull modulus of the 5Y specimens, indicating a narrower defect size distribution. SIGNIFICANCE: The study demonstrates that the impact of APA and RF treatments on the mechanical properties and reliability of VPP-fabricated 3Y-TZP and 5Y-PSZ ceramics is comparable to conventionally prepared zirconia. VPP technology for 3D printing provides a viable approach for future manufacturing of dental restorations with potential clinical applications.

Bonding Performance of Surface-Treated Zirconia Cantilevered Resin-Bonded Fixed Dental Prostheses: In Vitro Evaluation and Finite Element Analysis.

Debonding of zirconia cantilevered resin-bonded fixed dental prostheses (RBFDPs) remains the main treatment complication, therefore, the present in vitro study aimed to evaluate the effect of different surface pretreatments on the bonding of zirconia RBFDPs. Eighty milled zirconia maxillary central incisors, with complementary zirconia cantilevered RBFDPs, were randomly subjected to four different surface pretreatments (n = 20): as-machined (AM); airborne-particle abraded (APA); coated with nanostructured alumina coating (NAC); incisor air-abraded and RBFDP coated (NAC_APA). After bonding, half of each group (n = 10) was stored in deionized water (150 days/37 °C), thermocycled (37,500 cycles, 5-55 °C), and cyclically loaded (50 N/1.2 × 106). Load-bearing capacity (LBC) was determined using a quasi-static test. Additionally, finite element analysis (FEA) and fractography were performed. t-test and one-way ANOVA were used for statistical-analysis. Before aging, the NAC group provided superior LBC to other groups (p < 0.05). After aging, the AM specimens debonded spontaneously, while other groups exhibited comparable LBC (p ˃ 0.05). The FEA results correlated with the in vitro experiment and fractography, showing highly stressed areas in the bonding interface, cement layer, and in RBFDP's retainer wing and connector. The NAC RBFDPs exhibited comparable long-term bonding performance to APA and should be regarded as a zirconia pretreatment alternative to APA.

Rheological Properties and Setting Kinetics of Bioceramic Hydraulic Cements: ProRoot MTA versus RS.

Hydraulic calcium silicate-based cements (HCSCs) have become a superior bioceramic alternative to epoxy-based root canal sealers in endodontics. A new generation of purified HCSCs formulations has emerged to address the several drawbacks of original Portland-based mineral trioxide aggregate (MTA). This study was designed to assess the physio-chemical properties of a ProRoot MTA and compare it with newly formulated RS+, a synthetic HCSC, by advanced characterisation techniques that allow for in situ analyses. Visco-elastic behaviour was monitored with rheometry, while phase transformation kinetics were followed by X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared (ATR-FTIR), and Raman spectroscopies. Scanning electron microscopy with energy-dispersive spectroscopy, SEM-EDS, and laser-diffraction analyses was performed to evaluate the compositional and morphological characteristics of both cements. While the kinetics of surface hydration of both powders, when mixed with water, were comparable, an order of magnitude finer particle size distribution of RS+ coupled with the modified biocompatible formulation proved pivotal in its ability to exert predictable viscous flow during working time, and it was more than two times faster in viscoelastic-to-elastic transition, reflecting improved handling and setting behaviour. Finally, RS+ could be completely transformed into hydration products, i.e., calcium silicate hydrate and calcium hydroxide, within 48 h, while hydration products were not yet detected by XRD in ProRoot MTA and were obviously bound to particulate surface in a thin film. Because of the favourable rheological and faster setting kinetics, synthetic, finer-grained HCSCs, such as RS+, represent a viable option as an alternative to conventional MTA-based HCSCs for endodontic treatments.

Long-Term Stability of Hydrothermally Aged and/or Dynamically Loaded One-Piece Diameter Reduced Zirconia Oral Implants.

The aim of this in vitro study was to evaluate the long-term stability of one-piece diameter reduced zirconia oral implants under the influence of loading and artificial aging in a chewing simulator as well as the fracture load in a static loading test. Thirty-two one-piece zirconia implants with a diameter of 3.6 mm were embedded according to the ISO 14801:2016 standard. The implants were divided into four groups of eight implants. The implants of group DLHT were dynamically loaded (DL) in a chewing simulator for 107 cycles with a load of 98 N and simultaneously hydrothermally aged (HT) using a hot water bath at 85 °C. Group DL was only subjected to dynamic loading and group HT was exclusively subjected to hydrothermal aging. Group 0 acted as a control group: no dynamical loading, no hydrothermal ageing. After exposure to the chewing simulator, the implants were statically loaded to fracture in a universal testing machine. To evaluate group differences in the fracture load and bending moments, a one-way ANOVA with Bonferroni correction for multiple testing was performed. The level of significance was set to p < 0.05. In the static loading test, group DLHT showed a mean fracture load of 511 N, group DL of 569 N, group HT of 588 N and control group 0 of 516 N. The average bending moments had the following values: DLHT: 283.5 Ncm; DL: 313.7 Ncm; HT: 324.4 Ncm; 0: 284.5 Ncm. No significant differences could be found between the groups. Hydrothermal aging and/or dynamic loading had no significant effect on the stability of the one-piece diameter reduced zirconia implants (p > 0.05). Within the limits of this investigation, it can be concluded that dynamic loading, hydrothermal aging and the combination of loading and aging did not negatively influence the fracture load of the implant system. The artificial chewing results and the fracture load values indicate that the investigated implant system seems to be able to resist physiological chewing forces also over a long service period.

Influence of nanostructured alumina coating on the clinical performance of zirconia cantilevered resin-bonded fixed dental prostheses: Up to 3-year results of a prospective, randomized, controlled clinical trial.

STATEMENT OF PROBLEM: The debonding of zirconia cantilevered resin-bonded fixed dental prostheses remains a technical complication because zirconia's chemical inertness impedes adequate surface preparation for bonding. Limited clinical evidence on the performance of various pretreatment methods for the bonding surface of zirconia resin-bonded fixed dental prostheses is available. PURPOSE: The present prospective, randomized, controlled clinical trial aimed at evaluating the performance of zirconia resin-bonded fixed dental prostheses prepared with nanostructured alumina coating. MATERIAL AND METHODS: The study adopted a prospective, randomized, controlled, double-blind (patients, operator) design to compare the performance of nanostructured alumina coating with that of conventional airborne-particle abrasion. Twenty-seven healthy patients needing a replacement of a missing maxillary or mandibular central or lateral incisor were screened and rated to be eligible, and 31 zirconia cantilevered resin-bonded fixed dental prostheses were randomly allocated into 1 of 2 groups. The first group (n=15), where the restoration bonding surface was airborne-particle abraded with 50-µm alumina, served as a control group. In the second group (n=16), the restorations were pretreated with nanostructured alumina coating. Treatment and data collection were standardized. The primary outcome evaluated was the survival of the RBFDPs as defined by the restoration not debonding. The Kaplan-Meier analysis of cumulative survival was performed, and nonparametric tests were used to determine patient-specific differences between both study groups (age, sex, restored arch, tooth replaced, bonding surface area) (α=.05). Retainer wing surfaces of debonded resin-bonded fixed dental prostheses were inspected under a scanning electron microscope. RESULTS: Within a mean ±standard deviation observation period of 22.4 ±7.7 months (minimum, 8.3; maximum, 37.9 months), 3 debondings occurred, and the survival rate was 90.3%. The survival rate was 93.8% for the nanostructured alumina coating and 86.7% for the control group, with no statistically significant differences (log-rank, P=.54). No patient-specific differences were found between study groups (P>.05). As per the scanning electron micrographs, the majority of the nanostructured alumina-coated surfaces had large areas of nanostructured alumina residue, whereas the airborne-particle abraded surfaces exhibited predominantly adhesive failure with less cement residue. CONCLUSIONS: Over a mean observation period of 2 years, both zirconia pretreatments showed promising and comparable clinical results; therefore, nanostructured alumina coating could be regarded as a viable alternative pretreatment method to airborne-particle abrasion.

Effect of Two-Step Sintering on Properties of Alumina Ceramics Containing Waste Alumina Powder.

This study aims to evaluate the recycling potential of solid waste alumina powder (WAP) by utilization of the two-step sintering (TSS) process. For the study, WAP was collected as an industrial scrap after the machining process for the formation of green alumina compacts. The alumina samples were prepared according to the slip casting method by preparing suspensions containing commercial alumina with 0.8 µm average particle size and by adding up to 20 dwb. % (i.e., expressed on a dry weight basis) of WAP with 3.4 µm average particle size. The samples were sintered at optimized TSS conditions and compared with conventional one-step sintering (OSS) by conducting morphological analyses. The average grain size (AGS) was determined from the obtained field emission scanning electron microscopy (FESEM) images, while the sample porosity was calculated based on apparent densities. The obtained micrographs after TSS implementation revealed a partially textured microstructure. Furthermore, a comparison of the mechanical properties of alumina samples lacking or containing 20 dwb. % of WAP obtained after sintering is presented. The indentation fracture toughness (~3.2 MPa m1/2) and Vickers hardness data (~14.5 GPa) showed a positive effect of adding WAP to alumina samples. The slightly improved mechanical properties of ceramic samples containing waste alumina are a consequence of lower porosity, which is due to the remaining sintering additives in WAP. The collected results demonstrate the possibility of using TSS for sintering ceramic materials that contain WAP.

Zirconia fixed dental prostheses fabricated by 3D gel deposition show higher fracture strength than conventionally milled counterparts.

Zirconia restorations, which are fabricated by additive 3D gel deposition and do not require glazing like conventional restorations, were introduced as "self-glazed" zirconia restorations into dentistry. This in vitro investigation characterized the surface layer, microstructure and the fracture and aging behavior of "self-glazed" zirconia (Y-TZPSG) three-unit fixed dental prostheses (FDP) and compared them to conventionally CAD/CAM milled and glazed controls (Y-TZPC-FDPs). For this purpose, the FDPs were analyzed by (focused ion beam) scanning electron microscopy, laserscanning microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and a dynamic and static loading test. For the latter, half of the samples of each material group (n = 16) was subjected to 5 million cycles of thermocyclic loading (98N) in an aqueous environment in a chewing simulator. Afterwards, all FDPs were loaded to fracture. Y-TZPSG-FDPs demonstrated a comparable elemental composition but higher surface microstructural homogeneity and fracture strength compared to Y-TZPC-FDPs. Microstructural flaws within the FDPs' surfaces were identified as fracture origins. The high fracture strength of the Y-TZPSG-FDPs was attributed to a finer-grained microstructure with fewer surface flaws compared to the Y-TZPC-FDPs which showed numerous flaws in the glaze overlayer. A decrease in fracture strength after dynamic loading from 5165N to 4507N was observed for the Y-TZPSG-FDPs, however, fracture strength remained statistically significantly above the one measured for Y-TZPC-FDPs (before chewing simulation: 1923N; after: 2041N). Within the limits of this investigation, it can therefore be concluded that Y-TZPSG appears to be stable for clinical application suggesting further investigations to prove clinical applicability.

Clinical evaluation of monolithic zirconia multiunit posterior fixed dental prostheses.

STATEMENT OF PROBLEM: Monolithic zirconia restorations have been evaluated with in vitro studies, but limited clinical evidence of their longevity and reliability is available. PURPOSE: The purpose of this clinical study was to evaluate the clinical performance of posterior multiunit glazed monolithic zirconia fixed dental prostheses. MATERIAL AND METHODS: A total of 20 participants received 33 monolithic posterior zirconia fixed dental prostheses (Zolid white; Amann Girrbach AG) with minimally invasive preparations. Bilaterally supported fixed dental prostheses with a connector area of at least 9 mm2 were luted with resin-modified glass ionomer cement. The clinical evaluations were performed after 1 week, 6 months, and then annually after completion of the treatment. The biologic outcomes were evaluated by assessing the pocket depth, attachment level, plaque control, bleeding on probing, caries, and tooth vitality. Esthetics and the functional performance of the prostheses (color match, cavosurface marginal discoloration, anatomic form, marginal adaptation) were evaluated as per the rating scales of Cvar and Ryge. An analysis of survival was made by using the Kaplan-Meier method. RESULTS: After 39.8 ±16.7 months of observation, the overall survival rate of the monolithic zirconia multiunit posterior prostheses was 93.9%. No caries were found on the abutment teeth, signs of gingivitis were noted in 1 participant after 24 months, and increased probing depths of the abutment teeth were detected in 5 prostheses (15.1%). No loss of retention was detected. Two prostheses had to be replaced: 1 because of a biologic complication and 1 because of a technical complication. The remaining 31 prostheses received Alfa scores for marginal adaptation, cavosurface marginal discoloration, and caries. Twenty-seven (87.1%) prostheses were rated as Alfa and 4 (12.9%) as Bravo for anatomic form. The color match was noted as Alfa in 15 (48.3%) prostheses, and 16 (51.6%) were rated as Bravo. CONCLUSIONS: Monolithic zirconia restorations demonstrated a reliable treatment option after medium-term clinical use for the replacement of missing posterior teeth.

In vivo aging of zirconia dental ceramics - Part I: Biomedical grade 3Y-TZP.

OBJECTIVE: In vivo aging of biomedical grade 3Y-TZP ceramics in the oral environment was assessed and compared to artificially accelerated in vitro hydrothermal aging extrapolations at 37°C. METHODS: 88 discs were pressed and sintered (1450-1500°C) from two commercial 3Y-TZP compositions containing 0.25% Al2O3 to generate finer- and coarser-grained specimens. As-sintered (AS) and airborne-particle abraded (APA; 50µm Al2O3) surfaces were investigated. In vivo aging was performed by incorporating specimens in lingual flanges of complete dentures of 12 edentulous volunteers who wore them continuously for up to 24 months. For comparison, in vitro hydrothermal aging at 134°C was also performed and analysed by XRD and (FIB)-SEM. Data was statistically analysed with linear regression models. RESULTS: Finer and coarser-grained specimens exhibited statistically insignificant differences in aging in vivo. The monoclinic fraction (Xm) on AS surfaces abruptly increased to ∼8% after 6 months. The aging process then proceeded with slower linear kinetics (∼0.24%/month). After 24 months, Xm reached ∼12%. The calculated maximum transformed layer was 0.385µm representing one layer of transformed grains. APA surfaces were highly aging resistant. The initial Xm of ∼4.0% linearly increased by 0.03%/month in vivo. In vitro aging exhibited an initial induction period, followed by linear aging kinetics. Coarser-grained AS surfaces aged significantly faster than fine-grained (2.41%/h compared to 2.16%/h). APA discs aged at a rate of 0.3%/h in vitro. Microcracking within a single grain and pull-out of grain clusters were observed on aged AS surfaces. SIGNIFICANCE: Biomedical grade 3Y-TZP was susceptible to in vivo aging. After 2 years in vivo, the aging kinetics were almost 3-times faster than the generally accepted in vitro-in vivo extrapolation.

In vivo ageing of zirconia dental ceramics - Part II: Highly-translucent and rapid-sintered 3Y-TZP.

OBJECTIVE: 3Y-TZP ceramics with reduced alumina content have improved translucency and are used in monolithic dental restorations without porcelain-based veneers. The workflow can be further streamlined with rapid sintering. This study was designed to assess how these approaches affect ageing when the materials are exposed to the oral environment in vivo. METHODS: 43 discs were fabricated from 3Y-TZP powder with 0.05% Al2O3 and sintered with conventional or rapid regimens (1450 °C 2 h, 1530 °C 2 h, or 1530 °C 25 min). Their surfaces were polished or airborne-particle abraded with 50 µm Al2O3. The discs were incorporated in complete dentures of 16 volunteers and worn continuously for up to 48 months. Ageing changes on disc surfaces were monitored every 6 months by X-ray diffraction, scanning electron microscopy and atomic force microscopy. Data was statistically analysed with linear models. RESULTS: The amount of monoclinic phase on polished surfaces increased linearly, reaching up to 40% after 48 months in vivo. The ageing process observed for rapid sintering was 1.6 times faster compared to conventional sintering. A nano-scale increase in roughness with microcracking was also detected on polished surfaces. Airborne-particle abraded surfaces did not exhibit clear signs of ageing during the course of the study. SIGNIFICANCE: Highly-translucent 3Y-TZP ceramics are more susceptible to ageing than classic 3Y-TZP. After 4 years in vivo, the extent of degradation did not yet constitute grounds for clinical concern, but was more pronounced in materials prepared with rapid sintering.

Formation of Fe(III)-phosphonate Coatings on Barium Hexaferrite Nanoplatelets for Porous Nanomagnets.

Amorphous coatings formed with mono-, di-, and tetra-phosphonic acids on barium hexaferrite (BHF) nanoplatelets using various synthesis conditions. The coatings, synthesized in water with di- or tetra-phosphonic acids, were thicker than that could be expected from the ligand size and the surface coverage, as determined by thermogravimetric analysis. Here, we propose a mechanism for coating formation based on direct evidence of the surface dissolution/precipitation of the BHF nanoplatelets. The partial dissolution of the nanoplatelets was observed with atomic-resolution scanning transmission electron microscopy, and the released Fe(III) ions were detected with energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy in amorphous coating. The strong chemical interaction between the surface Fe(III) ions with phosphonic ligands induces the dissolution of BHF nanoplatelets and the consequent precipitation of the Fe(III)-phosphonates that assemble into a porous coating. The so-obtained porous nanomagnets are highly responsive to a very weak magnetic field (in the order of Earth's magnetic field) at room temperature, which is a major advantage over the classic mesoporous nanomaterials and metal-organo-phosphonic frameworks with only a weak magnetic response at a few kelvins. The combination of porosity with the intrinsic magneto-crystalline anisotropy of BHF can be exploited, for example, as sorbents for heavy metals from contaminated water.

Influence of surface airborne-particle abrasion and bonding agent application on porcelain bonding to titanium dental alloys fabricated by milling and by selective laser melting.

STATEMENT OF PROBLEM: Computer-aided design and computer-aided manufacturing (CAD-CAM) technologies have provided alternatives to lost-wax casting for the fabrication of titanium frameworks in metal-ceramic fixed dental prostheses (FDPs). The findings on varying metal surface characteristics resulting from application of different fabrication technologies indicate a need to reevaluate the traditional titanium surface conditioning protocols. PURPOSE: The purpose of this in vitro study was to investigate the effects of surface airborne-particle abrasion (APA) and bonding agent application on the porcelain bond to titanium dental alloys fabricated by subtractive computer numerical controlled (CNC) milling and by additive selective laser melting (SLM) methods. MATERIAL AND METHODS: Eight groups of Ti-6Al-4V substrates (n=11) were fabricated-half of them by CNC milling and half by SLM. The groups represented a fully crossed experimental protocol of APA with 110-µm Al2O3 particles under a pressure of 0.2 MPa (intact-controls or abraded) and bonding agent application (with or without bonding agent) for the CNC milled and SLM titanium substrates. Ultra-low fusing dental porcelain was applied to the differently prepared titanium substrates, and the titanium-ceramic bond strength was determined by a 3-point bend test according to the International Organization for Standardization (ISO) standard 9693-1:2012. Average profile roughness (Ra) values were obtained for intact and APA titanium substrates fabricated by CNC milling and by SLM. Representative titanium-ceramic interfaces were analyzed by using a field emission scanning electron microscope (FE-SEM) and energy dispersive spectroscopy (EDS). Titanium-ceramic bond strength data were analyzed statistically by 3-way ANOVA and the Tukey HSD test. Ra data were analyzed by 2-way ANOVA, followed by regression analyses (α=.05). RESULTS: The method applied for the digital fabrication of titanium (either subtractive CNC milling or additive SLM) did not affect the titanium-ceramic bond (P=.247). APA (P<.001), as well as the application of a bonding agent (P<.001), increased the titanium-ceramic bond strength. When these 2 procedures were combined, the porcelain bond strength to CNC milled titanium was 37.3 ±4.1 MPa and that to SLM titanium was 36.7 ±4.9 MPa. APA increased the surface roughness of CNC milled titanium (P=.002) but decreased the roughness of the SLM substrates (P<.001). CONCLUSIONS: A protocol comprising APA and application of a bonding agent ensures the highest porcelain bond strength to both CNC milled and SLM titanium, with the obtained values being well above the minimal value for metal-ceramic systems as specified by ISO 9693-1:2012.

TiN-Nanoparticulate-Reinforced ZrO2 for Electrical Discharge Machining.

This study presents a fabrication route for an electrically conductive ZrO2-TiN ceramic nanocomposite with a nanoscale TiN phase occupying ≤30 vol% to improve the mechanical reinforcement of the zirconia matrix, and at the same time provide electrical conductivity to facilitate electro-discharge machining (EDM). The TiN nanoparticles were incorporated into a 3 mol% yttria-stabilized tetragonal zirconia (Y-TZP) powder, either by admixing a TiN nanopowder (MCP) or by using in-situ synthesis (ISS) via the forced hydrolysis of a titanyl sulphate aqueous solution and the direct nitriding of as-synthesized titania nanoparticles, followed by consolidation and rapid sintering in a spark plasma sintering (SPS) system. The initial phase composition and crystal structure of the as-synthesized powders and the sintered samples were characterized by transmission electron microscopy (TEM) and X-ray difraction (XRD). The influence of the different fabrication routes on the microstructural evolution, electrical and mechanical properties, and affinity for EDM were assessed using TEM, focused ion beam scanning electron microscopy (FIB-SEM, Vickers indentation, electrical conductivity measurements, and profilometry. The MCP synthesis route resulted in finer microstructures that are less prone to microstructural inhomogeneities; however, using the ISS route, it was possible to fabricate electrically conductive Y-TZP nanocomposites containing only 15 vol% of the TiN nanoparticulate phase. Both synthesis routes resulted in an increase of the fracture toughness with an increase of the TiN phase due to the nanoparticulate TiN reinforcement of the Y-TZP ceramic matrix via crack-bridging toughening mechanisms. As both synthesis routes yielded Y-TZP nanocomposites capable of successful EDM machining at a TiN content of ≥30 vol% for the MCP and ≥ 15 vol% TiN for the ISS, a possible mechanism was developed based on the microstructure evolution and grain growth.

In situ generation of 3D graphene-like networks from cellulose nanofibres in sintered ceramics.

Establishing a 3D electrically percolating network in an insulating matrix is key to numerous engineering and functional applications. To this end, using hydrophobic carbon nanofillers is tempting, but still results in suboptimal performance due to processing challenges. Here, we demonstrate how natural cellulose nanofibres can be in situ transformed into graphene-like sheets connected to a 3D network enhancing both the transport and the mechanical properties of sintered engineering ceramics. The network architecture also permits the decoupling of electrical and thermal conductivities, which represents a major obstacle in attaining efficient thermoelectric materials. We foresee that our transferable methodology can pave the way for the use of natural nanofibres to unravel the full potential of 3D graphene-like networks to accelerate development in fields like energy and telecommunications.

Synthesis of Carbon-Nitrogen-Phosphorous Materials with an Unprecedented High Amount of Phosphorous toward an Efficient Fire-Retardant Material.

Phosphorus incorporation into carbon can greatly modify its chemical, electronic, and thermal stability properties. To date this has been limited to low levels of phosphorus. Now a simple, large-scale synthesis of carbon-nitrogen-phosphorus (CNP) materials is reported with tunable elemental composition, leading to excellent thermal stability to oxidation and fire-retardant properties. The synthesis consists of using monomers that are liquid at high temperatures as the reaction precursors. The molten-state stage leads to good monomer miscibility and enhanced reactivity at high temperatures and formation of CNP materials with up to 32 wt % phosphorus incorporation. The CNP composition and fire-retardant properties can be tuned by modifying the starting monomers ratio and the final calcination temperature. The CNP materials demonstrate great resistance to oxidation and excellent fire-retardant properties, with up to 90 % of the materials preserved upon heating to 800 °C in air.

The Hydrolysis of AlN Powder - A Powerful Tool in Advanced Materials Engineering.

The tendency for aluminium nitride (AlN) powder to undergo hydrolysis, which can lead to a complete degradation of the material, is unique in metal nitrides. Although this form of hydrolysis has been known for a long time, it is generally considered as a nuisance, because it prevents the aqueous powder processing of AlN-based ceramics. However, careful investigations of the course of hydrolysis, the reaction kinetics and the evolution of aluminium hydroxides have uncovered exceptional possibilities for the exploitation of this naturally driven process in the area of advanced materials engineering. It can be employed as superior synthesis path for hierarchically-assembled, mesoporous alumina powders or coatings consisting of 2D nanocrystalline lamellas. The beneficial surface characteristics of the powder serve as an ideal template for further modifications useful in catalysis, while the powder's flowability enables facile preparation of high-performance hierarchically porous structures. The coatings, on the other hand, are suitable as templates for superhydrophobic surfaces or as adhesive coatings for cementing zirconia dental ceramics. Finally, the hydrolysis-assisted solidification (HAS) process has proved to be an important asset in the processing science and technology for fabrication of porous and dense ceramics and nanocomposites.

Influence of thermo-mechanical cycling on porcelain bonding to cobalt-chromium and titanium dental alloys fabricated by casting, milling, and selective laser melting.

PURPOSE: The aim has been to determine the effect of thermo-mechanical cycling on shear-bond-strength (SBS) of dental porcelain to Co-Cr and Ti-based alloys fabricated by casting, computer-numerical-controlled milling, and selective-laser-melting (SLM). METHODS: Seven groups (n=22/group) of metal cylinders were fabricated by casting (Co-Cr and commercially pure-cpTi), milling (Co-Cr, cpTi, Ti-6Al-4V) or by SLM (Co-Cr and Ti-6Al-4V) and abraded with airborne-particles. The average surface roughness (Ra) was determined for each group. Dental porcelain was applied and each metal-ceramic combination was divided into two subgroups - stored in deionized water (24-h, 37°C), or subjected to both thermal (6000-cycles, between 5 and 60°C) and mechanical cycling (105-cycles, 60N-load). SBS test-values and failure modes were recorded. Metal-ceramic interfaces were analyzed with a focused-ion-beam/scanning-electron-microscope (FIB/SEM) and energy-dispersive-spectroscopy (EDS). The elastic properties of the respective metal and ceramic materials were evaluated by instrumented-indentation-testing. The oxide thickness on intact Ti-based substrates was measured with Auger-electron-spectroscopy (AES). Data were analyzed using ANOVA, Tukey's HSD and t-tests (α=0.05). RESULTS: The SBS-means differed according to the metal-ceramic combination (p<0.0005) and to the fatigue conditions (p<0.0005). The failure modes and interface analyses suggest better porcelain adherence to Co-Cr than to Ti-based alloys. Values of Ra were dependent on the metal substrate (p<0.0005). Ti-based substrates were not covered with thick oxide layers following digital fabrication. CONCLUSIONS: Ti-based alloys are more susceptible than Co-Cr to reduction of porcelain bond strength following thermo-mechanical cycling. The porcelain bond strength to Ti-based alloys is affected by the applied metal processing technology.

The influence of yttrium-segregation-dependent phase partitioning and residual stresses on the aging and fracture behaviour of 3Y-TZP ceramics.

The yttrium-segregation-dependent phase partitioning and residual stress development that influence both the aging and the fracture behaviour in 3Y-TZP bioceramics were studied by sintering alumina-free 3Y-TZP, varying the sintering temperature and the time, to yield ceramics with identical grain size distributions, but with different phase compositions. The structure and stability of the resulting tetragonal phases, in the form of transformable, yttria-lean t-ZrO2 (YLZ) and non-transformable, yttria-rich t″-ZrO2 and/or t'-ZrO2 (YRZ), were studied by X-ray diffraction (XRD) and focused ion beam scanning electron microscopy (FIB-SEM). The accelerated aging kinetics was fitted to the Mehl-Avrami-Johnson equation. The specimen sintered at the lowest sintering temperature but with the longest dwell time contained the smallest and the largest concentrations of yttria in the YLZ and YRZ phases, respectively, as well as the largest amount of YRZ. As a consequence, it exhibited the fastest linear aging kinetics accompanied by more extensive micro-cracking of the transformed layer, as well as largest amount of intergranular fracture and the greatest resistance to fracture. These properties were ascribed to the increased transformability of the YLZ phase and the greatest propensity of the YRZ phase to relax the accumulated residual stresses during transformation (tetragonal to monoclinic, t-m) manifested asa∼2.4% unit-cell volume increase. The observed relaxation provides additional understanding of the t-m transformation mechanism, which governs both the aging and fracture behaviour of 3Y-TZP. STATEMENT OF SIGNIFICANCE: A novel approach to understanding the effect of yttrium segregation on t-m transformation of 3Y-TZP zirconia bioceramics is presented. Carefully designed sintering strategy facilitated fabrication of ceramics with identical grain size distributions but with different yttrium concentrations. The influence of phase partitioning on stability and structure of transformable yttria-lean tetragonal phase (YLZ) and non-transformable yttria-rich phases (YRZ; t″- and t'-prime) and on the formation of residual stresses in YRZ were investigated. It is shown that YRZ phases are under compressive stresses in YLZ matrix, since a systematic relaxation after ageing was observed and explained for the first time. It puts additional perspective on the understanding of the t-m transformation mechanism ultimately governing both the ageing and fracture behaviour of 3Y-TZP.

The agglomeration, coalescence and sliding of nanoparticles, leading to the rapid sintering of zirconia nanoceramics.

Conventional sintering is a time- and energy-consuming process used for the densification of consolidated particles facilitated by atomic diffusion at high temperatures. Nanoparticles, with their increased surface free energy, can promote sintering; however, size reduction also promotes agglomeration, so hampering particle packing and complete densification. Here we show how the ordered agglomeration of zirconia primary crystallites into secondary particle assemblies ensures their homogeneous packing, while also preserving the high surface energy to higher temperatures, increasing the sintering activity. When exposed to intense electromagnetic radiation, providing rapid heating, the assembled crystallites are subjected to further agglomeration, coalescence and sliding, leading to rapid densification in the absence of extensive diffusional processes, cancelling out the grain growth during the initial sintering stages and providing a zirconia nanoceramic in only 2 minutes at 1300 °C.