Synergetic effects of SiC and Csf in ZrB2-based ceramic composites. Part II: Grain growth

The synergetic effects SiC particles and short carbon fibers (C_sf) as well as hot pressing parameters (sintering temperature, dwell time and applied pressure) on the grain growth of ZrB₂-based composites were investigated. Taguchi methodology was employed for the design of experiments to study the microstructure and grain growth of ZrB₂–SiC–C_sf ceramic composites. Three hot pressing parameters and SiC/C_sf ratio were selected as the scrutinized variables. The sintering temperature and SiC/C_sf ratio were identified by ANOVA as the most effective variables on the gain growth of ZrB₂-based samples. Removal of oxide impurities from the surface of starting particles by the reactant C_sf, not only hindered the extraordinary grain growth of ZrB₂ matrix, but also improved the sinterability of the ceramics. A fully dense ceramic with an average grain size of 8.3 µm was obtained by hot pressing at 1850 °C for 30 min under 16 MPa through adding 20 vol% SiC and 10 vol% C_sf to the ZrB₂ matrix. SEM observations and EDS analysis verified the in-situ formation of ZrC which can restrain the growth of ZrB₂ particles, similar to the role of SiC, by the pinning of grain boundaries as another stationary secondary phase.     

Reactive hot pressing of ZrB2-based composites with changes in ZrO2/SiC ratio and sintering conditions. Part I: Densification behavior

ZrB₂–SiC–ZrO₂ composites were hot pressed in order to investigate the effects of adding nano-sized ZrO₂ particles as well as the hot pressing parameters on the densification behavior of ZrB₂–SiC composites. An L9 orthogonal array of the Taguchi method was employed to study the significance of each parameter such as the sintering temperature, time, the applied external pressure, and ZrO₂/SiC volume ratio on the densification process. The statistical analyses revealed that among the mentioned parameters, the hot pressing temperature had a great influence over the densification. By being hot pressed at 1850 °C for 90 min under 16 MPa, fully dense ZrB₂-based composites were obtained. The relative density of the composites decreased at first and then enhanced as a function of ZrO₂/SiC ratio. Microstructural investigation of the fracture surfaces of the composites, which was carried out using the SEM analysis, showed the formation of new phases on the surfaces of SiC grains. The EDS and XRD analyses identified the ZrC as the newly formed interfacial phase due to the reaction between nano-ZrO₂ and SiC. The ZrC acted as an adhesive interphase between the ZrB₂/SiC grains, which could assist the sintering process.     

A hot-pressing reaction technique for SiC coating of carbon/carbon composites

A hot-pressing reactive sintering (HPRS) technique was explored to prepare SiC coating for protecting carbon/carbon (C/C) composites against oxidation. The microstructures of the coatings were analyzed by X-ray diffraction and scanning electron microscopy. The results show that, SiC coating obtained by HPRS has a dense and crack-free structure, and the coated C/C lost mass by only 1.84 wt.% after thermal cycles between 1773 K and room temperature for 15 times. The flexural strength of the HPRS-SiC coated C/C is up to 140 MPa, higher than those of the bare C/C and the C/C with a SiC coating by pressure-less reactive sintering. The fracture mode of the C/C composites changes from a pseudo-plastic behavior to a brittle one after being coated with a HPRS-SiC coating.     

Densification and high-temperature oxidation behavior of SiC sintered with multicomponent rare-earth additives

This study examined the effects of rare-earth (RE) elements such as Sc, Y, Ce, and Yb on the densification and oxidation of SiC. After adding binary or ternary RE nitrates in liquid form to β-SiC, hot pressing was performed at 1750 °C for 2 h under 20 MPa. RE nitrate was transformed into RE oxide and formed a liquid phase during sintering by a reaction with SiO₂ present on the SiC surface, where the total amount of RE oxide was fixed at 5 wt%. RE-based silicate melts acted as sintering additives without decomposing SiC at high sintering temperatures. SiC containing Sc–Y as an additive showed a much higher density (≥ 99%) than SiC containing the conventional Al–Y additive (∼95%). The multicomponent RE additive with a melting point (T_m) < 1550 °C had a relatively lower density than that with a higher T_m, owing to the evaporation of the additive at 1750 °C. The density of SiC also depended on the additive composition. The oxidation test, conducted at 1300 °C for up to 168 h in air, exhibited a parabolic weight gain. The SiC sample sintered with the Sc–Yb additive achieved the highest resistance of 3.23 × 10⁻⁵ mg/cm⁴·s.     

Oxidation of ZrC-30 vol% SiC composite in air from low to ultrahigh temperature

Oxidation of ZrC-30 vol.% SiC is investigated in air using furnace and oxyacetylene torch. The microstructure and phase composition of oxide scales are analyzed via SEM, XRD, and Raman. At 800 and 1100 °C, SiC is embedded in the porous and cracked ZrO₂ scales, which have a single-layer structure and are almost non-protective. At 1300 and 1500 °C, the protective effect of oxide scales is enhanced by the formed SiO₂. The scales consist of two subscales, outer and inner layers, during oxidation at 1300 °C for ≥1 h, and 1500 °C for ≥15 min. The growth kinetics of both layers is analyzed. At ∼1700 °C, a new layer is observed between the outer and inner layers, which should contain less carbon than the inner layer. At ∼2100 °C, the oxide scale is porous and contains many big holes. This scale shows a single-layer structure, which mainly consists of ZrO₂.     

Hot pressing of nanocrystalline zinc oxide compacts: Densification and grain growth during sintering

Sintering behavior of nanocrystalline zinc oxide (ZnO) powder compacts using hot pressing method was investigated. The sintering conditions (temperature and total time) and results (density and grain size) of two-step sintering (TSS), conventional sintering (CS) and hot pressing (HP) methods were compared. The HP technique versus CS was shown to be a superior method to obtain higher final density (99%), lower sintering temperature, shorter total sintering time and rather fine grain size. The maximum density achieved via HP, TSS and CS methods were 99%, 98.3% and 97%, respectively. The final grain size of samples obtained by HP was greater than that of TSS method. However, the ultra-prolonged sintering total time and the lower final density (88 ks and 98.3%) are the drawbacks of TSS in comparison with the faster HP (17 ks and 99%) method.     

Effect of open porosity on flexural strength and hardness of ZrB2-based composites

In this work, Taguchi L₃₂ experimental design was applied to optimize flexural strength and hardness of ZrB₂-based composites which were prepared by SPS. With this aim, batch ZrB₂-based composites tests were performed to achieve targeted experimental design with nine factors (SiC, C_f, MoSi₂, HfB₂ and ZrC content, milling time of C_f and SPS parameters such as temperature, time and pressure) at four different levels. Flexural strength of all composite was measured by three-point bending test. Hardness measurement was done by Vickers indenter. SEM was applied to evaluate microstructure. The results showed that SiC grain size plays important role on flexural strength and correlation between flexural strength and open porosity is low while hardness strongly depends to open porosity. Grain size variation in the range of ~1.5 µm to ~8 µm has little effect on hardness.     

Fabrication and mechanical behavior of ZrB2 strengthened SiCf/SiC composites prepared by hybrid processing route

A SiC fiber-reinforced composite containing a SiC-ZrB₂ mixed matrix (SiC_f/(SiC-ZrB₂)) with high density and enhanced mechanical properties was fabricated. ZrB₂ at 5 or 40?vol% was added to a (SiC + C) slurry to be infiltrated into the voids of 2D woven Tyranno?-SA grade-3 fabrics by electrophoretic deposition. Subsequent hot pressing at 1300?°C and 10?MPa for 1?h, followed by liquid silicon infiltration (LSI) at 1600?°C for 5?h in an Ar atmosphere resulted in the formation of the reaction-bonded SiC matrix, which revealed a composite density close to 97%. SiC_f/(SiC-ZrB₂) having open porosities of 0.2–0.6% showed peak strengths of 398 and 320?MPa for 5 and 40?vol% ZrB₂ addition, respectively. The large mismatch in the coefficient of thermal expansion and Young's modulus between the SiC and ZrB₂ phases was attributed to a reverse trend in the strength of composites. Brittle behavior of the composites in flexure can be explained by the strong bonding between the matrix and fibers formed by the reaction of interphase with molten Si during LSI. Strength retention after oxidation at 1000 and 1400?°C for 2?h was also compared in terms of ZrB₂ amount contained in the composites.     

Incorporation of BN-coated carbon fibers into ZrB2/SiBCN ceramic composites and their ablation behavior

ZrB₂/SiBCN composites containing carbon fibers coated with BN were prepared using combination of sol-gel and spark plasma sintering (SPS) techniques. Thermal shock and ablation behavior of these composites were thoroughly analyzed. Sintered composites contained ZrB₂, SiC and BN(C) crystalline phases. Thin BN layer passivated carbon fibers and prevented them from reacting with the matrix. With the addition of carbon fiber, diffusion coefficient decreased, and the thermal expansion coefficient increased in comparison to ZrB₂/SiBCN composites without carbon fibers. Ablation tests showed no crack formation after carbon fibers were added to the composites. Ablation center exhibited loose and porous network structure. ZrSiO₄ formed from ZrO₂ and SiO₂ reaction in the central ablation region. Presence of ZrSiO₄ prevented samples from further ablation-related damages.     

Fabrication of the tube-shaped SiCf/SiC by hot pressing

A manufacturing technique for fabricating a dense tubular SiC long fiber-reinforced SiC composite (SiC_f/SiC) by hot pressing was developed. After infiltrating a SiC-based matrix phase, containing a 12 wt% of Al₂O₃–Y₂O₃ sintering additive, into the fine voids of a Tyranno^TM-SA3 SiC fabric preform by electrophoretic deposition combined with the application of ultrasonic pulses, hot pressing was performed using 2 types of specially designed molds filled with graphite powder to transfer the vertical hot press force efficiently to the sidewalls of the tubular SiC_f/SiC. Compared to the low density (~60%) of SiC_f/SiC hot-pressed using a conventional mold, a density >95% could be acquired using a special mold filled with graphite powder as a pressure delivering medium. This method is suitable for fabricating a dense tubular SiC_f/SiC, which cannot be obtained using a conventional extrusion method.     

Theoretical and experimental analyses of relationship between processing and thermal conductivity of SiC with oxide additives

This paper analyzes theoretically and experimentally the thermal conductivity of the SiC-oxide additive-pore system. In the developed 6 model structures, the thermal conductivity of an SiC compact (κ_b) with oxide was calculated as functions of the volume fractions of SiC, oxide additive and pores. The calculated κ_b decreases in the order of a continuous phase where the other two particulate phases are dispersed: SiC>oxide additive>pores. The measured κ_b values of SiC compacts hot-pressed with 4–50 mass% oxide additive (mixture of 33.3 mass% Al₂O₃-33.3 mass% Y₂O₃-33.3 mass% SiO₂) were well explained by the calculated κ_b in two types of oxide continuous phase models. The thermal conductivities for only SiC grains in SiC compacts hot-pressed with 4 mass% Al₂O₃, Y₂O₃, SiO₂, Al₂O₃-Y₂O₃, Y₂O₃-SiO₂ and Al₂O₃-Y₂O₃-SiO₂ at 1950 °C were also estimated theoretically in the developed two model structures using the measured κ_b (oxide continuous phase model and SiC continuous phase model). Based on the calculated results, the following key factors are identified to achieve a high κ_b: (1) high sintered density, (2) a small amount of oxide additive with a high thermal conductivity, (3) no dissolution of foreign atoms from a liquid phase into SiC grains during solidification process.     

Densification improvement of spark plasma sintered TiB2-based composites with micron-, submicron- and nano-sized SiC particulates

Taguchi design of experiments methodology was used to determine the most influential spark plasma sintering (SPS) parameters on densification of TiB₂–SiC ceramic composites. In this case, four processing factors (SPS temperature, soaking time, applied external pressure and SiC particle size) at three levels were examined in order to acquire the optimum conditions. The statistical analysis identified the sintering temperature as the most effective factor influencing the relative density of TiB₂–SiC ceramics. A relative density of 99.5% was achieved at the optimal SPS conditions; i.e. temperature of 1800?°C, soaking time of 15?min and pressure of 30?MPa by adding 200-nm SiC particulates to the TiB₂ matrix. The experimental measurements and predicted values for the relative density of composite fabricated at the optimum SPS conditions and reinforced with the proper SiC particle size were almost similar. The mechanisms of sintering and densification of spark plasma sintered TiB₂–SiC composites were discussed in details.     

Formation, densification, and selected mechanical properties of hot pressed Al4SiC4, Al4SiC4 with 30 vol.% WC, and Al4SiC4 with 30 vol.% TiC

Powders of Al₄C₃ and SiC were combined by high-energy milling to produce Al₄SiC₄, Al₄SiC₄ + 30 vol.% TiC, and Al₄SiC₄ + 30 vol.% WC. Five different temperatures were used to hot press the constituents. XRD, SEM, relative density, and hardness measurements showed that formation of single-phase Al₄SiC₄ occurred at 1450 °C and full densification (99%) was achieved at 1500 °C. Both of these temperatures are lower than previously reported. Adding TiC and WC increases hardness, while WC improves densification (99.5%).     

Fabrication of Ti3SiC2-based composites via three-dimensional printing: Influence of processing on the final properties

In this work the influence of the processing routes on the microstructure and properties of Ti₃SiC₂-based composites was investigated. The three main processing steps are (i) three-dimensional printing of Ti₃SiC₂ powder blended with dextrin, (ii) pressing of printed samples (uniaxial or cold isostatic pressing), and (iii) sintering of pressed samples at 1600 °C for 2 h. The Ti₃SiC₂-based composites were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). Young's Modulus and flexural strength were measured to examine the mechanical properties. Porosity, density, shrinkage, and mass change were measured at each processing step. Those samples uniaxially pressed at 726 MPa presented the highest density, shrinkage, and mass change. However, microstructural morphologies were crack-free and homogeneous for cold isostatic pressed Ti₃SiC₂-based composites as compared to uniaxially pressed samples. The highest values for Young's Modulus (~300 GPa) and flexural strength (~3 GPa) were observed with uniaxially pressed Ti₃SiC₂-based composites.     

The effects of phenolic resin-derived PyC interlayers on microstructure and mechanical properties of Cf/SiC composites

A novel, easy and cost-effective way, infiltration and pyrolysis of phenolic resin solution, was exploited to prepare pyrolytic carbon (PyC) interlayers for carbon fiber/silicon carbide (Cf/SiC) mini-composites. X-ray photoelectron spectroscopy, dynamic contact angle measurement and scanning electron microscope were carried out to characterize chemical structure of carbon fibers (CFs), wetting properties between CFs and phenolic resin solution and microstructure of CFs and their composites, respectively. Remarkably, SEM results showed regulation of uniformity and thicknesses of PyC interlayer could be achieved through controlling the concentration of phenolic resin solution and oxidation condition of CFs. When CFs were treated by 10?min' oxidation with 40?mg/L ozone followed by dip-coating with 4?wt% phenolic solution, uniform PyC interlayer with approximately 120?nm were prepared on CFs. The corresponding Cf/SiC specimens had the largest increase in tensile strength and work of fracture with the improvement of 26.2% and 71.6% from the PyC-free case.     

Fabrication method and mechanical properties of biomimetic Cf/ZrB2-SiC ceramic composites with bouligand structures

Herein, biomimetic C_f/ZrB₂-SiC ceramic composites with bouligand structures are fabricated by combining precursor impregnation, coating, helical assembly and hot-pressing sintering. First, C_f/ZrB₂-SiC ceramic films are achieved through a precursor impregnation method using polycarbosilane (PCS). Second, the PCS-C_f/ZrB₂-SiC ceramic films are coated with ZrB₂ and SiC ceramic layers. Finally, hot-pressing sintering is employed to densify helical assembly C_f/ceramic films with a fixed angle of 30°. The microstructures and carbon fiber content on the mechanical properties of biomimetic C_f/ZrB₂-SiC ceramic composites are analyzed in detail. The results show that the coated ceramic layer on PCS-C_f/ZrB₂-SiC films can heal the cracks formed by pyrolysis of PCS, and the mechanical properties are obviously improved. Meanwhile, the mechanical properties could be tuned by the contents of the carbon fiber. The toughening mechanisms of C_f/ZrB₂-SiC ceramic composites with bouligand structures are mainly zigzag cracks, crack deflection, multiple cracks, carbon fiber pulling out and bridging.     

Fabrication of tubular SiCf/SiC using different preform architectures by electrophoretic deposition and hot pressing

This paper reports the processing feasibility of electrophoretic deposition combined with hot pressing in the fabrication of dense tubular SiC_f/SiC composites using a cylindrical mold. A simulation of pressure distribution using ANSYS software was performed by varying the angular inclinations in a cylindrical mold with an ‘out → in’ configuration so as to ensure a maximum and uniform conversion of vertical hot press force to the lateral side of a centrally-located preform through graphite powder. The simulation revealed an inhomogeneous pressure distribution along the height of the preform, which could be minimized by mold optimization to achieve a more uniform tube density. To verify this, two different preform architectures such as 0/90° woven 2-D fabric rolled in a jelly state and filament winding with two plies having an inter-ply angle of 55° were hot-pressed using a mold fabricated based on the simulation after infiltrating the matrix phase by electrophoretic deposition. The density of the tube could be increased with more uniform microstructures. Although the tube using a filament winding preform exhibited a lower flexural strength (105 MPa) and relative density (90%) than those with the preform rolled in a jelly state (221 MPa, 95%), the results revealed a high degree of fiber pull-out due to the PyC coating on the SiC fiber.     

Fatigue behavior and damage evolution of SiC/SiC composites under high-temperature anaerobic cyclic loading

In the present study, the fatigue behavior and damage evolution of SiC/SiC minicomposites at elevated temperatures in oxygen-free environment are investigated which are important for their application and are still unclear. The high-temperature fatigue test platform is developed and the fatigue stress-life curve and the stress-strain response are obtained. The test result shows that the life of the material at elevated temperature is shorter than that at room temperature under the same stress level. Moreover, the hysteresis loop width and the residual strain increase with the increasing of the cycles while the hysteresis modulus decreases during the fatigue cycling. The evolution process of matrix cracks is observed using the real-time remote detection system. It is found that matrix cracking is insensitive to the cyclic loading which is similar to room temperature and is due to that the degeneration of the interfacial shear stress reduces the area of high stress in matrix. The fiber/matrix interfacial shear stress under different cycles is determined based on the fatigue modulus of each hysteresis loop. The result shows a fatigue enhancement phenomenon for the interface which is not observed at room temperature.     

Preparation and properties of C/SiC/ZrO2 porous composites by hot isostatic pressing the pyrolyzed preforms

Three phase mixture of C/SiC/ZrO₂ porous composites were prepared from commercially available phenolic resin, Si and ZrO₂ powders. In the first step, mixed powders were pyrolyzed at 850 °C in vacuum to obtain a carbonized microporous material and then hot isostatically pressed at 1200, 1300 and 1350 °C for 10 min in an argon pressure of 50 MPa to prepare C/SiC/ZrO₂ porous composites, in second step. The hot isostatic pressing led to the increase in density from 3.28 to 3.48 g/cm³ and reduction in porosity (from 32 to 20%) of the composites. X-ray diffraction analyses revealed the existence of β-SiC and carbon might be amorphous in the composites. According to the results of scanning electron microscopy, the crystal growth of β-SiC with facets was observed at 1350 °C. In addition, the energy dispersive spectroscopy showed that carbon/silicon atomic ratio was 1:1 in the crystals. X-ray photoelectron spectroscopy of the composites suggested that evolved gaseous molecules, due to the decomposition of phenolic resin, reacted with molecules containing Si to form β-SiC. The formation and growth of β-SiC in addition to the densification of matrix by hot isostatic pressing led to the increase in hardness (max.: 13.99 GPa) at higher temperatures.     

Densification of nanosized amorphous and crystalline silicon nitride powders

The hot-pressing behavior of two amorphous and three crystalline silicon nitride powders, including both experimental and commercial samples has been investigated in the presence of MgO-Y₂O₃ sintering aid. The powders were characterized in terms of bulk and surface chemistry, phase composition and morphology. The sintering behavior was assessed on the basis of green and final densities, weight loss on densification and chemical and phase compositions of the dense material. ©