Development and evaluation of Al2O3–ZrO2 composite processed by digital light 3D printing

Digital Light Processing (DLP) is a promising approach to fabricate delicate ceramic components with high-fidelity structural features. In this work, the alumina and zirconia/alumina ceramic suspensions with low viscosity and high solid loading (40 vol%) were prepared specifically for DLP 3D printing. After debinding and sintering, the final parts were obtained without any defects. The surface morphologies and mechanical properties of alumina (Al₂O₃) and zirconia toughened alumina (ZTA) composites were investigated and the results showed that the final parts exhibited high relative densities and good interlayer combination at the sintering temperature of 1600 °C. Comparing with the Al₂O₃, the ZTA composites exhibited significantly enhanced density (99.4%), bending strength (516.7 MPa) and indentation fracture toughness (7.76 MPa m^1/2).     

Quantitative analysis of the residual stress and dislocation density distributions around indentations in alumina and zirconia toughened alumina (ZTA) ceramics

Alumina, 10% and 20% ZTA with 1.5 mol% yttria stabiliser were subjected to Vickers indentation testing with loads from 1 to 20 kg. Cr³⁺ fluorescence and Raman spectroscopy were applied to the indent centre and around the indentation in order to investigate the origin of the signal, the effect of indentation loads and zirconia phase transformation on the residual stress and plastic deformation in the plastic zone. The results suggested that with very strong laser scattering, the depth resolution of ZTA materials was very poor, which lead to a very significant amount of the signal being collected from the subsurface regions below the plastic zone. It was also found that zirconia phase transformation reduced the compressive residual stress in the alumina matrix within the plastic zone, except at the indentation centre, due to the tensile residual microstress generated by the zirconia phase transformation. In addition, the dislocation density on the indent surface of the ZTA samples was significantly reduced due to the restriction of crack propagation and energy absorption during the phase transformation process. At the indent centre, the zirconia phase transformation was suppressed by the high compressive stress, therefore, no significant difference between alumina and ZTA in terms of their residual stress and dislocation density were observed. Using TEM observation, it was found that the plastic zone microstructure of pure alumina is different from that of ZTA, which is consistent with the Cr³⁺ fluorescence results.     

Modelling of elastic modulus of a biphasic ceramic microstructure using 3D representative volume elements

In this work a methodology to reconstruct three-dimensional microstructures, representative of real biphasic ceramics using Neper free software is proposed. Finite element analysis in Ansys was implemented in order to calculate the effective elastic modulus of the simulated microstructures.Fine grained and dense zirconia toughened alumina (ZTA) materials with 5 and 40 vol.% of Yttria Stabilized Zirconia (YTZP) have been chosen to validate the proposed methodology. First, the effects of the size of the representative volume elements (RVEs) and the characteristics of the grain shapes are analysed. Second, the compliance with the isotropic condition is also verified.Agreement between the numerical and experimental values of the elastic modulus of the considered ZTA materials has been found. For these materials, zirconia fractions higher than 10 vol.% lead to bi-continuous microstructures which make the elastic properties deviate from the Voigt limit due to the increased number of contacts between zirconia grains.     

Microstructure and mechanical properties of alumina 5 vol% zirconia nanocomposites prepared by powder coating and powder mixing routes

Zirconia toughened alumina (ZTA) nanocomposites are attractive structural materials which combine the high hardness and Young's modulus of the alumina matrix with an additional toughening effect by the zirconia dispersion.In this study two approaches to prepare ZTA are compared. For the first approach, an ultrafine alumina powder was coated with 5 vol% zirconia by a wet chemical method. For the second one, the reference material was prepared by intensively mixing and milling the same alumina with nanoscale zirconia powder. Samples were consolidated at 1350–1600 °C by hot pressing and their mechanical properties, microstructure and transformation behavior were compared. Toughness increments derived from different toughening mechanisms are also briefly discussed. Besides better sinterability, the mixed material exhibited a finer grain size of both matrix and dispersion and thus higher hardness and strength. The alumina matrix was under compressive hydrostatic residual cooling stress, whereas zirconia was under tensile one. The coated material, however, showed higher transformability, deeper transformation zones and thus higher fracture toughness. In addition, it contained more monoclinic zirconia so the matrix was under tension.     

Hard and tough carbon nanotube-reinforced zirconia-toughened alumina composites prepared by spark plasma sintering

It is demonstrated that 0.1 wt% of multi-walled carbon nanotubes (MWCNTs) or single-walled carbon nanotubes (SWCNTs) added to zirconia toughened alumina (ZTA) composites is enough to obtain high hardness and fracture toughness at indentation loads of 1, 5, and 10 kg. ZTA composites with 0.01 and 0.1 wt% of MWCNTs or SWCNTs were densified by spark plasma sintering (SPS) at 1520 °C resulting in a higher hardness and comparable fracture toughness to the ZTA matrix material. The observed toughening mechanisms include crack deflection, pullout of CNTs as well as bridged cracks leading to improved fracture toughness without evidence of transformation toughening of the ZrO₂ phase. Scanning electron microscopy showed that MWCNTs rupture by a sword-in-sheath mechanism in the tensile direction contributing to an additional increase in fracture toughness.     

Properties of alumina 10 vol% zirconia composites—The role of zirconia starting powders

Zirconia toughened alumina (ZTA) materials are applied for cutting tools, wear parts and in biomedical applications. Due to the constraint of the rigid alumina matrix, ZTA materials with up to 10 vol% zirconia addition (AZ10) do not require addition of stabilizer oxides. AZ10 materials based on submicron sized alumina and four different submicron to nanoscale zirconia powders were manufactured by hot pressing at temperatures between 1475?1600 °C. Results show that the powder choice has a strong influence on mechanical properties, evolution of microstructure and phase composition. Best results with strength up to 850 MPa, fracture toughness values of 8.5 MPa√m and invulnerability to overfiring were obtained with zirconia powders showing the coarsest yet most homogeneous primary particle size and a low degree of agglomeration. Ultrafine but hard agglomerated powders lead to materials with extremely inhomogeneous microstructure and inferior properties.     

Electron beam physical vapour deposition and mechanical properties of c-ZrO2-ZTA-coatings on alloy 617 substrates

Multilayered zirconia toughened alumina (ZTA) and c-zirconia coatings were prepared using electron beam physical vapour deposition (EB-PVD). Characterizations of the morphology and chemical composition of the deposited coatings were performed using scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Scratch resistance, nano-indentation and bending strength were used for the evaluation of the mechanical properties. X-ray diffraction of the top ceramic TBC surface showed that it consists entirely of cubic ZrO₂ phase. The energy-dispersive X-ray spectroscopy analysis (EDS) showed that α-Al₂O₃ is the only oxide phase present at the interface, while SEM indicated the presence of columnar c-ZrO₂ as the only phase of the top coat. Delamination over a large region was observed in the case of double layer (ZTA) coating. In contrast, the multilayered (ZTA1 + ZTA2 + c-Z) coating showed neither delamination nor cracking. The hardness and scratch measurements showed that the top coat c-ZrO₂ layer is harder than the ZTA layers. The thermal conductivity of the multilayer coatings was estimated using the theoretical density and thermal conductivity values of zirconia toughened alumina (ZTA) and cubic-zirconia (c-ZrO₂) together with their experimentally measured data.     

Comparative ageing behaviour of commercial,unworn and worn 3Y-TZP and zirconia-toughened alumina hip joint heads

There is a trend today to develop zirconia toughened alumina (ZTA) composites for orthopaedic applications. So far, there is limited data concerning their sensitivity to ageing, especially considering tests performed on implants produced on an industrial scale. Here, complementary tools were used to assess the ageing resistance of ZTA femoral heads. The results were compared to femoral heads processed under the same industrial process with monolithic 3Y-TZP. As expected, monolithic 3Y-TZP implants exhibited significant ageing. In contrast ZTA femoral head showed no sign of degradation even over a period equivalent to that of a human life. The potential impact of coupling effects between wear and ageing is assessed. Monolithic zirconia and ZTA femoral heads were thus first worn in a hip joint simulator, and then aged in autoclave. The kinetics of transformation of the worn monolithic zirconia implants is accelerated while that of worn ZTA femoral heads remains almost unchanged.     

Mechanical and tribological properties of injection molded zirconia-alumina for orthopedic implants

Ceramics have gained great attention for hip and knee arthroplasty surgical procedures due to their ability to guarantee long-life performance in patients and are considered an alternative to existing metal systems.In the present study, zirconia toughened alumina (ZTA) for orthopaedic implants has been developed by Ceramic Injection Molding (CIM) process. Microstructural, mechanical and tribological studies have been carried out to establish whether the material is suitable for the purpose. The new CIM ZTA material obtained density up to 99.4%, toughness 6.1 MPa m^1/2, hardness 20 GPa, Young's modulus 320 GPa, and low coefficient of friction ranging between 0.08 and 0.13 under lubricated conditions, and between 0.11 and 0.34 in dry condition. To simulate the performance of the ZTA in vivo, i.e., the influence of material degradation on the ageing properties, accelerated hydrothermal aging was performed in vitro and good mechanical and tribological properties were confirmed for the developed ZTA.     

In situ study on microwave sintering of ZTA ceramic: Effect of ZrO2 content on densification,hardness, and toughness

Better understanding of the effect of multimode‐microwave sintering of zirconia‐toughened alumina (ZTA) was investigated. A comparative dilatometric analysis was conducted between conventional and microwave heating processes, to clarify the influence of zirconia on the densification of ZTA under electromagnetic field. The thermal gradient on sample measurements indicates the change to the microwave volumetric heating is improved by zirconia which adsorbs microwave energy better, thus acting as a susceptor. The most beneficial effect on microstructure, toughness, and hardness were observed at the optimal zirconia content of 10 vol%. The results with both microwave and conventional sintering illustrate the strengthening effect on the composite by zirconia. Of special interest, multimode microwave sintering creates a finer homogeneous microstructure, with resulting hardness and toughening comparable to those obtained for conventional sintering, as well as improved densification, and at lower cost.     

Synthesis of zirconia toughened alumina nanopowders as soft spherical granules by combining co-precipitation with spray drying

The nanopowders of zirconia toughened alumina (ZTA) as soft spherical granules were directly synthesized by combining co-precipitation with spray drying (CPSD). The co-precipitation of alumina (Al₂O₃) and yttria-stabilized zirconia (YSZ) was performed together in one step to obtain the ZTA precipitate. Spray drying, which is the most preferred industrial processing way to produce the nanopowders as spherical granules, was used to atomize, dry and granulate the suspension like milk prepared from the synthesized ZTA precipitate under previously optimized spray drying conditions. However, the important and complex processing parameters of spray drying such as the solid-liquid ratio and the feeding rate of the suspension, the inlet temperature and the flow rate of the hot air have to be optimized depending on the moll mass and volume of the component in the prepared suspension. The ZTA nanopowders containing 4–20 wt% YSZ synthesized by the CPSD method have a crystalline structure of alumina and YSZ, an average nanoparticle size between 26.64 and 46.70 nm with a very high specific surface area (SSA) between 77.43 and 112.41 m² g⁻¹ in a soft spherical granule form, which were determined by XRD, BET and SEM, respectively. The preparation and drying conditions of the synthesized precipitate, the solid-liquid ratio of the suspension and the molar mass ratio of YSZ in Al₂O₃ matrix have a significant effect on the crystallinity, morphology, particle size, SSA, and granule form of the synthesized ZTA nanopowders.     

Advancing spray granulation by ultrasound atomization

The influence of the atomization technique on the suitability of granules for dry pressing is the focus of the presented investigations. Therefore, destabilized alumina, zirconia, and zirconia toughened alumina (ZTA) slurries were spray dried and the obtained granules were used to fabricate green and finally sintered bodies for evaluation. Granules made in a laboratory spray dryer with a two-fluid nozzle served as a reference. An ultrasonic atomizer was integrated into the same spray dryer and the influence on the granule properties was evaluated. Untapped bulk density, granule size distribution, and flowability are among the evaluated granule-related properties as well as the granule yield which is used as an indicator of the process efficiency. Yield and flowability as most important granule properties are clearly improved when atomization is realized with ultrasound. The investigated sinter body properties include porosity, sinter body density, and biaxial strength and are as well positively affected by switching the atomization technique to ultrasound. Therefore, the approach to improve the compressibility of granules by ultrasonic atomization, which leads to an improved microstructure, density, and strength of sintered bodies, has proven to be successful for single-component ceramics (alumina and zirconia) as well as for the multicomponent ceramic ZTA.     

不同工艺制备ZrO2—Al2O3复合陶瓷超细粉体的研究

采用正滴定工艺，反滴定工艺和水解工艺来制备ＺｒＯ２－Ａｌ２Ｏ３系复合陶瓷超细粉体。研究了制备工艺对水合氧化锆凝胶的包裹状态，煅烧后粉体中ＺｒＯ２颗粒的弥散状态以及烧结体显微结构的影响。结果表明采用水解工艺，ＺｒＯ２颗粒能均匀弥散在Ａｌ２Ｏ３颗粒周围，最终获得均匀细晶的陶瓷烧结体；在反滴定工艺中，虽然水合氧化锆凝胶能较好包裹Ａｌ２Ｏ３颗粒，但由于Ａｌ２Ｏ３颗粒本身得不到有效分散，因此在烧结体中出现了     

FEM simulations of microstructure effects on thermoelastic properties of sintered ceramics

A model was developed to simulate macroscopic material properties of polycrystalline ceramics from the material properties of the constituting phases and the microstructure. Cubic and random structures were included. The model allows a variation of volume fractions of the phases, grain size and grain boundary areas. Representative for a large number of material properties, elastic tensor, thermal conductivity, coefficient of thermal expansion and thermal stress are calculated for individual microstructures using finite element methods (FEM). Simulations focus on two types of bi-continuous ceramic composites: zirconia toughened alumina (ZTA) and a porous zirconia ceramic which was infiltrated by a spinel-glass. Microstructure of experimental samples is represented by two different model structures: a Voronoi type structure for the ZTA ceramic and a cubic structure of cubes interconnected by cylinders for the infiltrated zirconia system. A substantial impact of microstructure on macroscopic material properties and internal stress distribution is obtained. A good agreement between measured and simulated material properties was found.     

Combined zirconia toughened alumina (ZTA) stacks obtained by electron beam physical vapour deposition

Ion assisted electron beam physical vapour deposition (EB-PVD) technique was used for three zirconia toughened alumina (ZTA) batches containing 15, 25, 35, mole% ZrO₂ and c-zirconia ceramic multilayer deposition on 617-Ni based alloy substrate. The ceramic batches were prepared via sol-gel technique. The thickness of the coated layers was found to be 0.66 μm for ZTA layers and 0.65 μm for c-zirconia layer. Evaluation of the microstructure of the samples coated with c-zirconia on the top of different ZTA coats reveals three different regions. First region indicates c-ZrO₂ coat, second region exhibits ZTA layers, while third is the metallic substrate. The top coat microstructure can be divided into two zones. The inner zone (ZTA zone), which is the early part of multiple nucleation and subsequent growth of the columnar microstructure. The outer zone (c-ZrO₂) which is crystallographically perfect columnar YSZ coatings produced by EB-PVD.     

Electroconductive composite of zirconia and hybrid graphene/alumina nanofibers

Novel type of hybrid nanofillers representing graphene encapsulated alumina nanofibres was selected as an additive to develop toughened electroconductive partially stabilized zirconia. The sinterability, mechanical and electrical properties of the produced nanocomposites were studied as function of the filler/graphene content. Composites containing just 0.6 vol.% of graphene corresponding to 3 vol.% of hybrid nanofibres exhibited high electroconductivity of 58 S/m without deterioration of mechanical properties. They also showed a slight toughening effect that is reflected by an increase in the indentation fracture toughness by 20% as compared to monolithic zirconia.     

Charge trapping characteristics of alumina based ceramics

The space charge dynamics is very important for electrical breakdown of alumina based ceramics. In this paper, the charge trapping/detrapping characteristics of alumina based ceramics were studied by means of isothermal surface potential decay (ISPD) method. For alumina and zirconia toughened alumina (ZTA) ceramic samples, the ISPD curves charged by corona discharge as well as microstructure characterization were carried out. For the first time, crossover phenomenon and hollow shaped potential profile were observed and reported in alumina based ceramics, indicating a surface potential decay process dominated by charge injection and volume conduction affected by the trap states in materials. In addition, the comparative trapping characteristics were evaluated based on a charge detrapping controlled decay model. The correlation between trap distribution and microstructure of alumina based ceramics was investigated. It was proposed that different charge trapping characteristics of alumina based ceramic samples was caused by varied shallow trap density of grain boundary.     

微波处理条件下含氧化钇稳定氧化锆增韧氧化铝陶瓷中的相变行为研究

本文采用XRD方法对微波热处理前后具有不同含量的氧化钇稳定氧化锆增韧氧化铝陶瓷的相变行为进行了研究。实验结果表明微波处理过程中,低含量Y_2O_3稳定ZTA陶瓷表面几乎皆为单斜相,当Y_2O_3含量超过2mol％时则四方相含量剧增,其原因在于ZTA陶瓷微波处理引起体积性加热造成较大的内外温差,使得内应力缓解了基质对ZrO_2的约束而发生t—ZrO_2=m—ZrO_2相变。同时如果调节稳定剂含量适中(如2mol％Y_2O_3),并对瓷体进行微波特殊处理后可获得较高的断裂相变量,有利于相变增韧陶瓷力学性能改善及损伤部件的性能自回复。     

Manufacturing and deformation behavior of alumina and zirconia helical springs at room temperature

Ceramic helical springs with identical dimensions were produced by hard machining from alumina, alumina toughened zirconia (ATZ), and tetragonal zirconia polycrystals (TZP) stabilized with different oxides. According to the results of the spring constant determination under deformation rates of 3 mm/min, the deformation behavior of all ceramic springs obeys to Hook's law. However, variation of the deformation rate, tests under constant load, and spring recovery behavior revealed differences in the deformation behavior of alumina, TZP, and ATZ springs. Alumina springs exhibited time-independent deformation in all tests. In contrast, anelastic deformation at room temperature was demonstrated in all springs containing TZP. This deformation is completely reversible over a period of several days. Anelastic behavior is particularly pronounced in Y-TZP springs, whereas Ce-TZP springs exhibit comparatively very low but still reliably detectable anelasticity. Oxygen vacancies in the TZP ceramic are considered the most likely explanation for the anelastic behavior of TZP springs at room temperature.     

Pressureless sintering of gelcast ZTA–MgO–TiO2 systems as potential dental ceramics

Abstract

Abstract

The pressureless sintering behaviour of gelcast zirconia toughened alumina (ZTA) containing the total 5 wt-% additives of MgO and TiO₂ was investigated. The effects of four combinations of MgO and TiO₂ on the bulk properties, morphology and phase composition of the ZTA composites were evaluated in comparison with pure ZTA in the temperature range of 1150–1600°C. Four combinations of MgO and TiO₂ initiated effective densification and enhancement at 1450°C, as indicated by the relative density and three-point bending strength measurements and fracture morphological observations by using scanning electron microscopy. X-ray diffraction analyses confirmed that the difference in the bending strength among four groups of ZTA composites was due to the MgO dependent formation of minor MgAl₂O₄ and TiO₂ induced polymorphic transformation of tetragonal phase to monoclinic ZrO₂. These results are useful to further develop dental ceramics, including glass infiltrated ZTA.