Thermal shock behavior of porous Si3N4 ceramics with Nd2O3 as sintering additive

The thermal shock behavior of porous Si₃N₄ ceramics with Nd₂O₃ as sintering additive was investigated by the water quenching method in the temperature difference range from 200 to 1500°C. The porosity and residual flexural strength of the specimens after single water quenching were measured to reveal the influence of thermal shock on porous Si₃N₄ ceramics. It was found that the critical temperature was 780°C, which was almost 230°C higher than its dense counterpart reported by other researchers. Scanning electron microscope was used to examine the microstructure evolution of the external surface and interior after water quenching. Surface oxidation and cracks formation were found to be the primary cause of the strength degradation of porous Si₃N₄ ceramics. The phase composition variation in the surface was also characterized by X-ray diffraction.     

Fabrication,thermal shock resistance,and dielectric property of α-Si3N4-based ceramic coating on porous Si3N4 ceramics

A dense α-Si₃N₄-based ceramic protective coating was successfully prepared on porous Si₃N₄ ceramics by a liquid infiltration and filling method. The coating composed of a primary α-Si₃N₄ phase and secondary O'-Sialon, β-Sialon, and Y–Si–Al–O–N glass phase. After thermal shock at ΔT = 1000°C for five times, cracks were produced, but the tip of crack stopped inside the coating; so the coated porous Si₃N₄ ceramics still had a good waterproof ability and its water absorption was only 7%. During thermal shock, toughening mechanisms involving needle-like O'-Sialon particle bridging, crack deflection, and rough fracture, occurred within the cracks, contributing to thermal shock resistance of the coating. The dielectric constant of the coated porous Si₃N₄ ceramics showed a slow increase trend with increasing temperature, and it reached the maximum value of 3.57 at 1100°C at the frequency of 11 GHz. The dielectric loss increased slowly as the temperature increased from room temperature to 900°C, but it started to increase evidently when the temperature was over 900°C.     

Effects of heat treatment on mechanical properties of 3D Si3N4f/BN/Si3N4 composites by PIP

The fabrication of three-dimensional silicon nitride (Si₃N₄) fiber-reinforced silicon nitride matrix (3D Si₃N_4f/BN/Si₃N₄) composites with a boron nitride (BN) interphase through precursor infiltration and pyrolysis (PIP) process was reported. Heat treatment at 1000–1200 °C was used to analyze the thermal stability of the Si₃N_4f/BN/Si₃N₄ composites. It was found after heat treatment the flexural strength and fracture toughness change with a pattern that decrease first and then increase, which are 191 ± 13 MPa and 5.8 ± 0.5 MPa·m^1/2 respectively for as-fabricated composites, and reach the minimum values of 138 ± 6 MPa and 3.9 ± 0.4 MPa·m^1/2 respectively for composites annealed at 1100 °C. The influence mechanisms of the heat treatment on the Si₃N_4f/BN/Si₃N₄ composites include: (Ⅰ) matrix shrinkage by further ceramization that causes defects such as pores and cracks in composites, and (Ⅱ) prestress relaxation, thermal residual stress (TRS) redistribution and a better wetting at the fiber/matrix (F/M) surface that increase the interfacial bonding strength (IBS). Thus, heat treatment affects the mechanical properties of composites by changing the properties of the matrix and IBS, where the load transfer efficiency onto the fibers is fluctuating by the microstructural evolution of matrix and gradually increasing IBS.     

Effect of BN content on microstructures,mechanical and dielectric properties of porous BN/Si3N4 composite ceramics prepared by gel casting

Porous BN/Si₃N₄ composite ceramics with different BN contents have been fabricated by gel casting. The rheological behaviors of the suspensions, microstructure, mechanical properties, dielectric properties and critical temperature difference of thermal shock (ΔT_C) of porous BN/Si₃N₄ composite ceramics with different BN contents were investigated. With BN contents increasing, the mechanical properties of the porous BN/Si₃N₄ composite ceramics were partially declined, but the dielectric properties and thermal shock resistances were enhanced at the same time. For the porous Si₃N₄ ceramic without BN addition, the porosity, flexural strength, dielectric constant and critical temperature difference were 48.1%, 128 MPa, 4.1 and 395 °C, while for the 10 vol% BN/Si₃N₄ porous composite ceramics, they were 49.4%, 106.6 MPa, 3.8, and 445 °C, respectively. The overall performance of the obtained porous BN/Si₃N₄ composite ceramics indicated that it could be one of the ideal candidates for high-temperature wave-transparent applications.     

Thermal shock resistance of Al2O3/SiO2 composites by sol-gel

In this paper, the SiO₂ ceramic matrix composites were reinforced by the two-dimensional (2D) braided Al₂O₃ fibers by sol-gel. To develop the high performance aeroengine with excellent resistance to thermal shock for advanced aerospace application, two different thermal shock temperatures (1100?°C and 1300?°C) and three different thermal shock cycles (10, 20 and 30 cycles) were tested and compared in this paper; besides, the thermal shock resistance of Al₂O₃/SiO₂ composites was investigated in air. Our results suggested that, the flexural strength of the untreated composites was 78.157?MPa, while the residual strength of Al₂O₃/SiO₂ composites under diverse thermal shock cycles and temperatures had accounted for about 95% and 50% of the untreated composites, respectively. Meanwhile, the density and porosity of the composites were gradually increased with the increase in test temperature. Moreover, the changes in fracture morphology and micro-structural evolution of the composites were also observed. Our observations indicated that, the fracture morphology of the composites mainly exhibited ductile fracture at the thermal shock temperature of 1100?°C, whereas brittle fracture at the thermal shock temperature of 1300?°C. Additionally, Al₂O₃/SiO₂ composites belonged to the Oxide/Oxide CMCs, so no new phase was formed after thermal shock tests. Above all, findings of this paper showed that Al₂O₃/SiO₂ composites had displayed outstanding thermal shock resistance.     

Influence of ZrO2 Content on the Performances of BN‐ZrO2‐SiC Composites for Application in the Steel Industry

BN‐ZrO₂‐SiC composites were fabricated with different ZrO₂ contents ranging from 0 to 40 vol%. The mechanical properties and corrosion resistance against molten steel increase with increasing ZrO₂ content, while thermal shock resistance decreases gradually. When ZrO₂ content is 40 vol%, the flexural strength is 346 MPa and corrosion depth is 254 μm. The improved corrosion resistance is attributed that the corrosion layer formed by residual ZrO₂ hinders molten steel penetration. Nevertheless, composite with 40 vol% ZrO₂ shows a sharp decline in residual flexural strength when temperature difference is more than 400°C and critical temperature difference is 520°C.     

Effect of magnesium aluminum silicate glass on the thermal shock resistance of BN matrix composite ceramics

The effects of magnesium aluminum silicate (MAS) glass on the thermal shock resistance and the oxidation behavior of h‐BN matrix composites were systematically investigated at temperature differences from 600°C up to 1400°C. The retained strength rate of the composites rose with the increasing content of MAS showing a maximum value at the 60 wt% MAS. Compared with the original strength, the retained strength of the specimen after thermal shock increased to 77% (ΔT=1000°C). The strengthening effect of MAS and the surface microstructural evolution of composites are responsible for the improved thermal shock resistance. Surface oxidation of the composites during the thermal shock process plays a positive role in enhancing the retained strength by self‐healing cracks and the appearance of the compressive stress. The oxide layer also acted as a thermal barrier to decelerate the actual thermal stress. Furthermore, this dense layer also improved the oxidation resistance of h‐BN matrix composites by prevent diffusion of oxygen. These results indicated that short‐term surface oxidation during thermal shock process is favorable to the enhancement of the thermal shock resistance of BN‐MAS composite ceramics.     

Self-propagating high temperature synthesis (SHS) of porous Si3N4-based ceramics with considerable dimensions and study on mechanical properties and oxidation behavior

The aim of present work is to fabricate porous Si₃N₄ ceramics with considerable dimensions and homogeneous microstructure by self-propagating high temperature synthesis (SHS) using Si, Si₃N₄ diluent and Y₂O₃ as raw materials. The results indicate that Si₃N₄ diluent with coarse particle sizes and appropriate β-phase content is beneficial to obtain porous Si₃N₄ ceramics with homogeneous microstructure and excellent mechanical property by controlling the shrinkage inside the sample. The produced Si₃N₄ ceramics possessed excellent flexural strength of 168 MPa～259 MPa, and high Weibull modulus of 11.0～17.2. Additionally, BN and SiC are added as second phase to modify the properties of Si₃N₄-based ceramics. Optimum flexural strength of 170 MPa and 137 MPa were obtained with 10 wt.% addition of BN and SiC respectively. After oxidation at 1100 °C～1300 °C, second phase-doped Si₃N₄ ceramics also presented higher residual strength than pure Si₃N₄ ceramics.     

Comparative evaluation of two different methods for thermal shock resistance of laminated ZrB2-SiCw/BN ceramics

The thermal shock resistance (TSR) of laminated ZrB₂–SiC_w/BN ceramic was evaluated through indentation-quench and quenching-strengthening methods. It was correspondingly compared to monolithic ZrB₂–SiC_w ceramic. In the indentation-quench method with consideration to crack propagation on the surface layer, the critical thermal shock temperature of laminated ZrB₂–SiC_w/BN ceramic with surface residual tensile stress was 550?°C, which was lower than monolithic ZrB₂–SiC_w ceramic (600?°C). Unlike the microscopic method of crack growth measurement through indentation-quench testing, the quenching-strengthening method, which was based on the macroscopic properties of the material, mainly characterizing the residual strength subsequently to thermal shock, the critical thermal shock temperatures of the laminates and monolithic were 609?°C and 452?°C, respectively. Compared to the brittle fracture of ZrB₂–SiC_w ceramics, the deflection, bifurcation and delamination of the cracks as the main TSR mechanisms of the laminated ceramics, were revealed through quenching-strengthening method, which was more suitable for the TSR characterization of laminated ceramics.     

Microstructure and EMW absorption properties of CVI Si3N4–SiCN ceramics with BN interface annealed in N2 atmosphere

A kind of chemical vapor infiltration (CVI) Si₃N₄–BN–SiCN composite ceramic with excellent electromagnetic wave (EMW) absorbing properties is obtained by CVI BN interface and SiCN matrix on porous Si₃N₄ ceramics, and then annealed at high temperatures (1200°C‐1500°C) in N₂ atmosphere. The crystallization behavior, EMW absorbing mechanism and mechanical properties of the composite ceramics have been investigated. Results showed CVI SiCN ceramics with BN interface were crystallized in the form of nanograins, and the crystallization temperature was lower. Moreover, both EMW absorbing properties and mechanical properties of CVI Si₃N₄–BN–SiCN composite ceramics firstly increased and then decreased with the increase in annealing temperature due to the influence of BN interface on the microstructure and phase composition of the composite ceramics. The minimum reflection coefficient (RC) and maximum effective absorption bandwidth (EAB) of the composite ceramics annealed at 1300°C were ?47.05 dB at the thickness of 4.05 mm and 3.70 GHz at the thickness of 3.65 mm, respectively. The flexural strength and fracture toughness of the composite ceramics annealed at 1300°C were 94 MPa and 1.78 MPa/m^1/2, respectively.     

Comparative investigation of ultrafast thermal shock of Ti3AlC2 ceramic in water and air

In this work, ultrafast thermal shock of Ti₃AlC₂ ceramic was evaluated in water and air by utilizing the induction heating method. First, the annealed samples were heated to the set temperature in tens of seconds and dropped into the cooling water within 0.1 s which is rather short not to degrade the sample temperature. Compared to the traditional thermal shock method when quenching in water, the abnormal thermal shock phenomenon did not occur, which is owing to that no dense oxide layers were formed on the samples’ surface to act as the thermal barrier. The continuous decrease in residual flexural strength when quenched in water is associated with water infiltration, chemical reaction, and large surface tensile stress. The residual strength has 27.25 MPa upon 1250°C. Second, at the same testing temperature, the residual flexural strength when quenched in air maintains a high value of 388 MPa up to 1400°C. Dense oxide scales existed on the quenched surface of Ti₃AlC₂ samples. The results exhibit that Ti₃AlC₂ ceramic possesses excellent thermal shock resistance in water and air, suitable to be applied in extreme environments.     

Microstructural evolution during thermal shock process and the residual strength of Si3N4 ceramics

Thermal shock resistance of silicon nitride was investigated from aspects of residual strength and microstructure, using a water quenching method. The residual strengths after 800 and 1000°C thermal shock polarized as higher ones and much lower ones, and reasons for the huge disparity are explored. With heat treatment temperature getting higher, the inner small pores rush to and aggregate in the surface layer of the samples. When the heat treatment reaches 1400°C, a darker subsurface layer is observed, which is caused by the loss of most Al and Y elements. Moreover, many more small pores are found in this layer, acting as the dissipation sources, they protect the material strength by releasing the intense thermal stress. But this subsurface layer disappears during the natural cooling down to 600°C as Al and Y uniformly redistributed in extended oxidation, then huge cracks form on the surface layer undergoing much smaller thermal stress from 600 to 0°C. Moreover, the bonding Y and Si can be oxidized into two types of Y₂Si₂O₇ crystals that improve the thermal shock performance of Si₃N₄.     

Light‐weight thermal insulating fly ash cenosphere ceramics

Light weight fly ash cenosphere (FAC) ceramic composites were developed by simple slip casting method. Thermal properties, Bulk density, Microstructure, flexural strength, and phase analysis of the FAC ceramic composites were measured. The results proved that the FAC have ability to lower bulk density and thermal conductivity effectively. The lowest thermal conductivity achieved for FAC ceramic composites (0.27 W/m.K) was further reduced 0.21 W/m.K by adding combustible additives ie activated charcoal and corn starch. The flexural strength, bulk density and thermal conductivity of FAC ceramic composites reduced consistently with an increase in FAC content. The maximum flexural strength of 13.45 MPa was achieved with 50% FAC and the minimum flexural strength of 4.07 MPa was obtained with 80% FAC. The open porosity increased from 35.51% to 43.76% and 38.19% with an addition of 15% activated charcoal and corn starch, respectively, when compared to no additives. The bulk density of 699, 619, and 675 kg/m³ was achieved with 80% FAC, 80% FAC with the addition of 15% activated charcoal and corn starch, respectively. The 80% FAC ceramic composite shows low thermal expansion coefficient 6.54 × 10^?6/°C at the temperature of 50°C then it varies between 3.7 and 5 × 10^?6/°C in the temperature range above 100°C. These results prove that the developed light weight FAC ceramic are excellent low‐cost thermal insulating materials.     

Effects of pore diameters on phase,oxidation resistance,and thermal shock resistance of the porous Si2N2O ceramics

Porous silicon oxynitride (Si₂N₂O) ceramics were prepared by gas pressure sintering at 1650°C for 2 hour under 1.5 MPa N₂ in two different powder beds, that is, h‐BN/Si₃N₄ or h‐BN/(Si₃N₄ + SiO₂). Effects of the gaseous atmosphere in the powder bed and the pore diameter in the ceramics on formation of the Si₂N₂O phase and the oxidation resistance of the sintered porous ceramics were investigated. Results showed that presence of the gaseous SiO in the powder bed played a crucial role in suppressing decomposition of the Si₂N₂O phase at the outer surface of the material. Permeability of the gaseous substances was decreased when the pore diameter was small, to affect the phase composition and the oxidation behavior of the porous Si₂N₂O ceramics. The oxidation weight gain curves of the porous Si₂N₂O ceramics fitted the asymptotic law. No significant changes in the dielectric constant of the Si₂N₂O ceramics were observed after oxidation at 1000°C‐1200°C for up to 30 minutes, whereas the dielectric loss tangent was reduced by oxidation due to formation of SiO₂. The as‐obtained porous Si₂N₂O ceramics could withstand a highest thermal shock of 1200°C when the outer surface could be sealed by the oxidation‐derived SiO₂ layer.     

High-temperature mechanical property and thermal shock resistance of Al2O3f/Al2O3 composites

Continuous alumina fiber–reinforced alumina matrix composites (Al₂O_3f/Al₂O₃ composites) were produced via sol–gel process, then the high-temperature mechanical property and thermal shock resistance of Al₂O_3f/Al₂O₃ composites were investigated. The results showed that the composites exhibited excellent high-temperature properties. The mechanical property of the composites was affected by heat treatment (prepared at 1100°C exhibited the most desirable mechanical property). The tensile strength of the composites abruptly decreased at higher temperatures. Although the mechanical property of the composites deteriorated after the thermal shock test was conducted at high temperatures, they exhibited excellent thermal shock resistance. After 50 thermal shock tests conducted at 1300 and 1500°C, the flexural strength of the composites was found to be 124.34 and 93.04 MPa, thus showing a decrease in strength with the increasing temperature.     

Crystallization Behavior of Amorphous Si2BC3N Ceramic Monolith Subjected to High Pressure

The crystallization behavior of amorphous Si₂BC₃N monoliths by heating at 1000°C–1400°C and 5 GPa was investigated with the special attention to the nucleation mechanisms of β‐SiC and BN(C) phases. Nanoscale puckered structures arising in particle bridging areas were found and its evolution behavior well reflected the nucleation process of nanocrystallites. The temperature‐dependent crystallization of amorphous Si₂BC₃N monoliths at 5 GPa passes through four stages: The material remains amorphous below 1100°C. It undergoes partial phase segregation (1100°C–1200°C), followed by initiation of nucleation (1200°C–1250°C), and then nucleation and growth of β‐SiC and turbostratic BN(C) crystallites (>1250°C). The first principles calculation indicates the nucleation precedence of BN(C) phase over β‐SiC. BN(C) nucleates preferentially at bridges between ceramic particles causing SiC to concentrate in particle interiors thus forming capsule‐like structures.     

Temperature-dependent mechanical and oxidation behavior of in situ formed ZrN/ZrO2-containing Si3N4-based composite

In this work, Si₃N₄ and Zr(NO₃)₄ were used as raw materials to prepare ZrN/ZrO₂-containing Si₃N₄-based ceramic composite. The processing, phase composition, and microstructure of the composite were investigated. Hardness and fracture toughness of the ceramics were evaluated via Vickers indentation in Ar at 25°C, 300°C, 600°C, and 900°C. During spark plasma sintering, Zr(NO₃)₄ was transformed into tetragonal ZrO₂, which further reacted with Si₃N₄, resulting in the formation of ZrN. The introduction of ZrN enhanced the high-temperature mechanical properties of the composite, and its hardness and fracture toughness reached 13.4 GPa and 6.1 MPa·m^1/2 at 900°C, respectively. The oxidation experiment was carried out in air at 1000°C, 1300°C, and 1500°C for 5 h. It was shown that high-temperature oxidation promoted the formation and growth of porous oxide layers. The microstructure and phase composition of the formed oxide layers were investigated in detail. Finally, it was identified that the obtained composite exhibited a higher thermal diffusivity than that of monolithic Si₃N₄ in the temperature range of 100°C–1000°C.     

Silicon nitride/boron nitride ceramic composites fabricated by reactive pressureless sintering

Using Si and BN powders as raw materials, silicon nitride/hexagonal boron nitride (Si₃N₄/BN) ceramic composites were fabricated at a relatively low temperature of 1450 °C by using the reaction bonding technology. The density and the nitridation rate, as well as the dimensional changes of the specimens before and after nitridation were discussed based on weight and dimension measurements. Phase analysis by X-ray diffraction (XRD) indicated that BN could promote the nitridation process of silicon powder. Morphologies of the fracture surfaces observed by scanning electron microscopy (SEM) revealed the fracture mode for Si₃N₄/BN ceramic composites to be intergranular. The flexural strength and Young's modulus decreased with the increasing BN content. The reaction-bonded Si₃N₄/BN ceramic composites showed better machinability compared with RBSN ceramics without BN addition.     

Effect of MgF2 addition on sinterability and mechanical properties of fluorapatite ceramic composites fabricated by wollastonite and phosphate glass

In this paper, we successfully report the design and synthesis of fluorapatite ceramic composites using phosphate glass and wollastonite as raw materials via a simple sintering method. The effects of MgF₂ additives in phase composition, microstructure, densification, and mechanical properties are investigated at various temperatures from 600 °C to 900 °C, and characterized by SEM/EDS, XRD, FTIR, linear shrinkage and water absorption, flexural strength analysis. It shows that the densification and mechanical behavior of composites increase with both the sintering temperature and MgF₂ content. Especially, the sample SCPF-7 exhibits the highest densification and optimal mechanical properties at 900 °C. At these conditions, the water absorption of fluorapatite ceramic composite is less than 0.20%, and the flexural strength is over 70 MPa. For the microstructure analysis, the formation of fluorapatite with a rod-like microstructure is enhanced with the increase of MgF₂ content. The amelioration of these properties is due to the formation of a new phase which helps to the formation of compact microstructure. The findings in this work provide a feasible strategy for the preparation of fluorapatite ceramic composites from available phosphate glass and wollastonite at a lower temperature.     

Experiments and transient finite element simulation of γ-Y2Si2O7/B2O3-Al2O3-SiO2 glass coating on porous Si3N4 substrate under thermal shock

A dense γ-Y₂Si₂O₇/B₂O₃-Al₂O₃-SiO₂ glass coating was fabricated by slurry spraying method on porous Si₃N₄ ceramic for water resistance. Thermal shock failure was recognized as one of the key failure modes for porous Si₃N₄ radome materials. In this paper, thermal shock resistance of the coated porous Si₃N₄ ceramics were investigated through rapid quenching thermal shock experiments and transient finite element analysis. Thermal shock resistance of the coating was tested at 700 °C, 800 °C, 900 °C and 1000 °C. Results showed that the cracks initiated within the coating after thermal shock from 800 °C to room temperature, thus leading to the reduction of the water resistance. Based on the finite element simulation results, thermal shock failure tended to occur in the coating layer with increasing temperature gradient, and the critical thermal shock failure temperature was measured as 872.24 °C. The results obtained from finite element analysis agree well with that from the thermal shock tests, indicating accuracy and feasibility of this numerical simulation method. Effects of thermo-physical properties for the coating material on its thermal shock resistance were also discussed. Thermal expansion coefficient of the coating material played a more decisive role in decreasing the tangent tensile stress.