Strength degradation and failure limits of dense and porous ceramic membrane materials

Thin dense membrane layers, mechanically supported by porous substrates, are considered as the most efficient designs for oxygen supply units used in Oxy-fuel processes and membrane reactors. Based on the favorable permeation properties and chemical stability, several materials were suggested as promising membrane and substrate materials: Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ, La_0.6?xSr_0.4Co_0.2Fe_0.8O_3?δ (x = 0, 0.02) and Ce_0.9Gd_0.1O_1.95?δ. Although membranes operate at elevated temperatures, the ends of tubes in certain three-end concepts remain almost at room temperature. The current work concentrates on the failure potential of these membrane parts, where in a complex device also the highest residual stresses should arise due to differences in thermal expansion. In particular, sensitivity of the materials to subcritical crack growth was assessed since the long-term reliability of the component does not only depend on its initial strength, but also on strength degradation effects. The results were subsequently used as a basis for a strength–probability–time lifetime prediction.     

Comparison of conventional Knoop and Vickers hardness of ceramic materials

Ceramics generally have a lower Knoop than Vickers hardness. This difference is due to the elastic recovery occurring around a Knoop indentation and the difference in representative area considered to calculate the hardness value.Conventional hardness tests with Knoop and Vickers indenters were performed in order to show how Knoop hardness test can give the same hardness number obtained by Vickers hardness test. This is obtained when Knoop hardness number is calculated based on the residual plastically deformed area whether projected or true. Complementary hardness data obtained from the literature were used in this work in order to validate the method proposed in this work. A revision of the well-known relation of Marshall is proposed in order to determine the elastic modulus by means of one Knoop hardness test when the Vickers hardness is unknown.     

Mechanical properties of porous MgO substrates for membrane applications

Advanced design concepts for the application of oxygen transport ceramic membranes are based on thin layers supported by porous substrates. One suitable support material in this respect is porous MgO. However, a careful consideration of the mechanical stability is required to warrant long term performance and reliability under application relevant thermo-mechanical loads. The current work summarizes the effect of the sintering conditions on porosity and mechanical properties and gives elastic modulus and fracture stress as a function of temperature. An enhancement of the strength by the addition of boehmite to MgO was tested. Elastic moduli are determined and compared as obtained by indentation and bending tests. With respect to fracture, specimens in planar geometry are investigated using ring-on-ring bending tests; tubes are tested using an O-ring set-up. Fracture stresses are statistically analyzed. The obtained mechanical parameters are compared to that of other potential porous substrate materials.     

Mechanical characterization of porous Ba0.5Sr0.5Co0.8Fe0.2O3−d

The mechanical stability of porous Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−d (BSCF) material was investigated using depth-sensitive microindentation and ring-on-ring biaxial bending tests. The porous BSCF was characterized as potential substrate material for the deposition of a dense membrane layer. Indentation tests yielded values for hardness and fracture toughness up to a temperature of 400 °C, while bending tests permitted an assessment of elastic modulus and fracture stress up to 800 °C. In addition the fracture toughness was evaluated up to 800 °C measuring in bending tests the fracture stress of pre-indented specimens. The results proof that the indentation-strength method can be applied for the determination of the fracture toughness of this porous material. In comparison to dense material the values of the mechanical parameters were as expected lower but the temperature dependences of elastic modulus, fracture strength and toughness were similar to those reported for dense BSCF.     

Mechanical properties of tape casted Lanthanum Tungstate for membrane substrate application

Advances in the development of asymmetric membrane concepts require the development of porosity optimized, mechanically reliable substrate materials. The current study focuses on the characterization of the room temperature mechanical properties of tape casted Lanthanum Tungstate of different porosities for membrane substrate applications. Elastic modulus and hardness are assessed using indentation testing. Characteristic strength and Weibull modulus are determined from data obtained using a ball-on-3-balls test that is particularly advantageous for the rather thin tape casted material. Particular emphasis is placed on the effect of the surface composition onto the fracture strength.     

Mechanical properties of cBN-Al composite materials

The relationship between microstructure and mechanical properties for a wide range of composite materials based on polycrystalline cubic boron nitride and aluminium as a binder phase (PcBN-Al) has been examined. The PcBN-Al composites were made using high-pressure, high-temperature (HPHT) sintering methods, yielding materials with grain sizes of cBN between 2 and 20 μm and an initial amount of Al binder between 15 and 25 vol.%. Hardness ranged between 15 and 40 GPa, while fracture toughness and strength were between 6.4-8.0 MPa m^1/2 and 355-454 MPa, respectively. Fractography was employed to investigate the large scatter in fracture strengths and correlate fracture strength with fracture toughness through the size of the fracture origins.     

Mechanical properties of zirconia composite ceramics

Composite materials based on 8 wt% yttria partially stabilized zirconia, with additions of gadolinium zirconate, lanthanum lithium hexaaluminate, yttrium aluminum garnet and strontium zirconate were characterized. Samples were fabricated by hot-press sintering at 1550 °C. The effect of the secondary phase content on the mechanical properties of the composites was evaluated. Hardness, elastic modulus and fracture toughness of the fabricated composites were determined by means of depth-sensitive indentation testing. The fracture toughness of the samples as determined by the indentation method was found to increase with increasing YSZ content, reaching 3 MPa·m^0.5 for samples with 80 wt% YSZ. The fracture toughness appeared to be affected by thermal expansion coefficient mismatch, crack bridging and crack deflection.     

Mechanical and tribological properties of TiB2-SiC and TiB2-SiC-GNPs ceramic composites

TiB₂-SiC and TiB₂-SiC-graphene nanoplatelets (GNPs) composites were prepared using field-assisted sintering technology at 2100 °C in argon atmosphere, and the influence of the SiC and different GNPs addition on microstructure development, mechanical and tribological properties has been investigated. Instrumented hardness, bending strength, chevron-notched fracture toughness and ball-on-flat tribological tests were used for the testing and characterization of the composites. The addition of SiC significantly improved the bending strength and elastic modulus with values of 601 MPa and 474 GPa, respectively, but decreased the fracture toughness with a value of 4.8 MPa.m^1/2. The addition of GNPs has a positive effect on fracture toughness and flexural strength but a negative one on the hardness. The increasing amount of both GNPs has a positive influence on wear characteristics of the composites thanks to the described wear mechanisms.     

Mixed-mode fracture model to quantify local toughness in nacre-like alumina

With the progress of ceramic engineering, tough technical ceramics such as nacre-like alumina now exhibit complex fracture patterns with high degrees of deflection, branching and bridging. If these mechanisms highly contribute to improving crack resistance, the crack geometries go beyond the hypotheses assumed in standard techniques to quantify toughness, making it difficult to understand the mechanisms responsible for crack propagation. We report a robust local solution based on a combination of analytical formulas and finite element analysis to accurately estimate the effective stress intensity factors at the tips of multiple deflected cracks. The influence of sample size on local R-curves is analysed and shown to be less important relative to standard methods. We use this method to evaluate the direct influence of zirconia nanoparticles in the nacre-like structure and highlight the role of these findings in the understanding of mechanical response and future optimisation of highly textured tough ceramics.     

Strength characterization of tubular ceramic materials by flexure of semi-cylindrical specimens

Mechanical strength at elevated temperatures and operating atmospheres needs to be characterized during development of tubular ceramic components for advanced energy technologies. Typical procedures are time-consuming because a large number of tests are required for a reliable statistical strength characterization and every specimen has to be subjected to the process conditions individually. This paper presents an efficient strength characterization methodology for tubular ceramics. The methodology employs flexure of semi-cylindrical specimens as the strength test and implements the tests within a facility capable of loading multiple specimens in controlled environments. The stress field is analyzed in detail with finite element analyses. The validity of the test is found to depend on specimen dimensions and the valid range is established. The methodology is demonstrated by experimental measurements conducted on oxygen transport membrane materials at room temperature and 850 °C.     

Toughening cement-based materials through the control of interfacial bonding

Mortars are made from inherently brittle components: sand grains and hardened cement paste. Under normal circumstances, cracks will propagate rapidly through the cement matrix, bypassing the strong sand grains but fracturing some of the weakest. The approach of the work described in this paper was to modify the mortar in order to alter this process. These modifications produced tensile residual stresses between the matrix and the aggregate, which when released by an additional applied tensile stress produced microcracking, debonding of matrix from aggregate, a small expansion and increased toughness. This work demonstrates toughening in sand/Portland cement mortars modified with different expansive admixtures: sodium sulphate or dead-burnt lime. Additionally, mortars of sand/ASTM Type K cement were tested. In order to give additional insight into the toughening mechanism, spherical and angular aggregate have been used to ascertain the consequences of microcracking and aggregate-bridging. The role of aggregate-bridging, especially when related to fracture paths, is also discussed and suggests that the bond between the aggregate and the matrix has been found in some cases to control not only the crack path but consequently the apparent toughness.     

The effect of an oxygen partial pressure gradient on the mechanical behavior of perovskite membrane materials

In application of perovskite as oxygen conducting materials the membrane is operated at elevated temperatures under an oxygen gradient. The effect of the partial pressure difference on the mechanical properties is reported in the current work. Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) and La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) samples were annealed under an oxygen gradient. The mechanical properties of cross-sections were characterized using indentation testing. Chemical strains for BSCF and LSCF were too small to detect them after cooling to RT by XRD; however, the results suggest that the indentation crack length is affected by chemical strains for LSCF, but not for BSCF. An anisotropy of the indentation crack length and corresponding apparent fracture toughness is related with the interaction of domain switching and residual strain that is probably also associated with the observation that vacuum (10⁻⁵ mbar) annealed LSCF showed surface cracking on heating in air, whereas for BSCF such fracture features were not observed.     

Influence of the elastic mismatch on the Hertzian cone crack path in ceramic bilayers

Contact damage is a key aspect in the structural integrity of ceramics, particularly ceramic coatings and multilayers that may have an elastic mismatch. An understanding of the critical load and trajectories of the crack produced by contact loads in such materials is valuable to characterize the damage tolerance and improve their reliability. In this work, the Hertzian cone crack initiation and propagation in brittle bilayers has been studied by FEM and verified by experimental observations. It was concluded that the elastic mismatch affects the crack initiation position and critical load for cone cracking. Critical loads are lower in bilayers than in monolithic materials. Cone crack trajectory and the corresponding fracture energy release rate are also affected by the elastic mismatch, which thus influences the damage tolerance of the system.     

Improvement of mechanical performances and characteristics of bulk Bi-2212 materials exposed to Au diffusion and stabilization of durable tetragonal phase by Au

This study centers sensitively on the determination of optimum diffusion annealing temperature (650–850 °C) for the electrical, superconducting, crystal structure, and especially mechanical characteristics of Au surface-layered Bi-2212 superconducting materials with the aid of dc electrical resistivity, powder X-ray diffraction and microhardness measurements. The experimental results show that all the characteristic properties (normal state resistivity, critical transition temperatures, degree of broadening, phase fractions, lattice cell parameters, elastic modulus, yield strength, fracture toughness, brittleness index and flexural strength parameters) improve considerably with the increment in the annealing temperature up to 800 °C as a consequence of the decreased local structural distortions, lattice strains, disorders, defects and grain boundary interaction problems in the Cu-O₂ consecutively stacked layers. After the critical annealing temperature value of 800 °C, the parameters immediately recrudesce towards their global minimum points. Similarly, the highest Bi-2223 phase fraction and c-axis length are observed at the 800 °C annealing temperature due to the best crystallinity and crystal plane alignments. Additionally, the optimum value strengthens the mechanical durability and ideal flexural strength as a result of the stabilization of durable tetragonal phase. Thus, the presence of Au impurities increases the critical stress value so that the crack-producing flaws and cracks propagation divert or slow down rapidly. On the other hand, the excess temperature value such as 850 °C leads to the deleterious effect on the mechanical performances of Au surface-layered Bi-2212 compound because of the increased residual porosity and omnipresent flaws (stress raisers and crack initiation sites). Further, it is at least equally important that the crack propagation or dislocation movement more proceeds through the transgranular regions instead of along the intergranular regions with increasing temperature up to the optimum value beyond which the limited number of operable slip systems enhances noticeably and the intergranular fracture becomes more dominant.     

Mechanical and thermal behavior of cellular mullite materials

In this paper, the mechanical behavior and thermal properties of cellular mullite bodies obtained by thermal direct-consolidation of foamed aqueous suspensions of mullite-bovine serum albumin (BSA) and mullite-BSA-methylcellulose (MC) were studied. The mechanical behavior of cellular mullite materials sintered at 1600 °C was evaluated by diametral compression at room temperature, 1000 °C and 1300 °C. The variation in the thermal diffusivity and thermal conductivity at temperatures up to 900 °C was determined using the laser-flash method. The results of the mechanical and thermal evaluation were analyzed based on the porosity features of the sintered materials, which was determined in turn by the starting system used for shaping the bodies.     

Mechanical activation-assisted autoclave processing and sintering of HfB2-HfO2 ceramic powders

This study reports on the synthesis and consolidation of HfB₂-HfO₂ ceramic powders via mechanical activation-assisted autoclave processing followed by pressureless sintering (PS) or spark plasma sintering (SPS). HfCl₄, B₂O₃ and Mg starting powders were mechanically activated for 5 min to obtain homogeneously blended precursors with active particle surfaces. Autoclave synthesis was carried out at a relatively low temperature at 500 °C for 6 or 12 h. As-synthesized powders were purified from reaction by-products such as MgO and MgCl₂ by washing and acid leaching treatments. The characterization investigations of the as-synthesized and purified powders were performed by using an X-ray diffractometer (XRD), stereomicroscope (SM), scanning electron microscope (SEM) and particle size analyzer (PSA). The purified powders with an average particle size of about 190 nm comprised the HfB₂ phase with an amount of 79.6 wt% in addition to the HfO₂ phase and a very small amount of Mg₂Hf₅O₁₂ phase after mechanical activation for 5 min and autoclave processing for 12 h. They were consolidated at 1700 °C both by PS for 6 h and SPS for 15 min. The Mg₂Hf₅O₁₂ phase decomposed during sintering and bulk samples only had the HfB₂ and HfO₂ phases. The bulk properties of the sintered samples were characterized in terms of microstructure, density, microhardness and wear characteristics. The HfB₂-HfO₂ ceramics consolidated by PS exhibited poor densification rates. A considerable improvement was obtained in the relative density (~91%), microhardness (~16 GPa) and relative wear resistance (2.5) values of the HfB₂-HfO₂ ceramics consolidated by SPS.     

Polymer derived silicon oxycarbide ceramic monoliths: Microstructure development and associated materials properties

Polymer derived SiOC and SiCN ceramics (PDCs) are interesting candidates for additive manufacturing techniques to develop micro sized ceramics with the highest precision. PDCs are obtained by the pyrolysis of crosslinked polymer precursors at elevated temperatures. Within this work, we are investigating PDC SiOC ceramic monoliths synthesized from liquid polysiloxane precursor crosslinked with divinylbenzene for fabrication of conductive electromechanical devices. Microstructure of the final ceramics was found to be greatly influenced by the pyrolysis temperature. Crystallization in SiOC ceramics starts above 1200?°C due to the onset of carbothermal reduction leading to the formation of SiC and SiO₂ rich phases. Microstructural characterisation using ex-situ X-ray diffraction, FTIR, Raman spectra and microscopy imaging confirms the formation of nano crystalline SiC ceramics at 1400?°C. The electrical and mechanical properties of the ceramics are found to be significantly influenced by the phase separation with samples becoming more electrically conducting but with reduced strength at 1400?°C. A maximum electrical conductivity of 10¹ S?cm^?1 is observed for the 1400?°C samples due to enhancement in the ordering of the free carbon network. Mechanical testing using the ball on 3 balls (B3B) method revealed a characteristic flexural strength of 922?MPa for 1000?°C amorphous samples and at a higher pyrolysis temperature, materials become weaker with reduced strength.     

Mechanical and thermal expansion properties of Dy2TiO5 ceramic neutron absorbers with small grains

Dy₂TiO₅ ceramics with small grain size range of 1.5–3 μm were successfully prepared by microwave sintering method. The phase composition, microstructure, thermal expansion, stability, corrosion resistance and neutron absorption properties of Dy₂TiO₅ ceramics were investigated. The results show that Dy₂TiO₅ ceramics possess high mechanical properties due to the small grain size, with a microhardness of 12.26 GPa. The addition of Mo significantly reduces the thermal expansion phenomenon of the sample. The oxide film formed on the surface of the Dy₂TiO₅ ceramic enhances its excellent corrosion resistance. In addition, the Dy₂TiO₅ ceramic shows excellent neutron absorption with 87.34% neutron absorption and over 94% thermal neutron absorption in 8 cm thick particles.     

Mechanical properties of graphene platelet-reinforced alumina ceramic composites

Alumina (Al₂O₃) ceramic composites reinforced with graphene platelets (GPLs) were prepared using Spark Plasma Sintering. The effects of GPLs on the microstructure and mechanical properties of the Al₂O₃ based ceramic composites were investigated. The results show that GPLs are well dispersed in the ceramic matrix. However, overlapping of GPLs and porosity within ceramics are observed. The flexural strength and fracture toughness of the GPL-reinforced Al₂O₃ ceramic composites are significantly higher than that of monolithic Al₂O₃ samples. A 30.75% increase in flexural strength and a 27.20% increase in fracture toughness for the Al₂O₃ceramic composites have been achieved by adding GPLs. The toughening mechanisms, such as pull-out and crack deflection induced by GPLs are observed and discussed.     

Mechanical investigation of weak regions in a wound oxide-oxide ceramic matrix composite

The main aim of the investigation was to quantify the influence of production-related cross-lines on static mechanical properties (tensile, flexural and shear) of an oxide-oxide CMC as a comparison between specimens with cross-lines and specimens without cross-lines in tested regions. Investigated material was a weak-matrix oxide-oxide CMC (WHIPOX?) made of Nextel? 610 fibers (3000 denier) and alumina matrix with a special winding pattern. Mechanical tests at room temperature revealed that cross-lines were local weak regions in a wound component. Spatial separation of the cross-line within the composite (2?mm shift from layer to layer) did not improve the negative influence of the cross-lines on mechanical properties. Fractographic investigations revealed that cross-lines acted as a trigger of material failure.