Spark plasma sintering of quadruplet ZrB2–SiC–ZrC–Cf composites

Spark plasma sintering (SPS) route was employed for preparation of quadruplet ZrB₂–SiC–ZrC–C_f ultrahigh temperature ceramic matrix composites (UHTCMC). Zirconium diboride and silicon carbide powders with a constant ZrB₂:SiC volume ratio of 4:1 were selected as the baseline. Mixtures of ZrB₂–SiC were co-reinforced with zirconium carbide (ZrC: 0–10 vol%) and carbon fiber (C_f: 0–5 vol%), taking into account a constant ratio of 2:1 for ZrC:C_f components. The sintered composite samples, processed at 1800 °C for 5 min and 30 MPa punch press under vacuumed atmosphere, were characterized by densitometry, field emission scanning electron microscopy, energy dispersive spectroscopy, X-ray diffractometry as well as mechanical tests such as hardness and flexural strength measurements. The results verified that the composite co-reinforced with 5 vol% ZrC and 2.5 vol% C_f had the optimal characteristics, i.e., it reached a relative density of 99.6%, a hardness of 18 GPa and a flexural strength of 565 MPa.     

Effect of short carbon fiber content on the mechanical properties of TiB2-based composites prepared by spark plasma sintering

In this study, TiB₂-30 vol% SiC composites containing 0, 5, 10, and 15 vol% short carbon fibers (C_f) were produced by spark plasma sintering (SPS). The effect of carbon fiber content on microstructure, density, and mechanical properties (micro-hardness and flexural strength) of the fabricated composites was studied. Scanning electron microscopy (SEM) results indicated that the fibers were uniformly dispersed in the TiB₂–SiC matrix using wet ball milling before SPS process. Fully dense TiB₂–SiC–C_f composites were achieved by SPS process at 1900°C for 10 min under 30 MPa. With the addition of fibers, the relative density of the composites did not change considerably. Mechanical tests revealed that microhardness was reduced about 19% by the incorporation of carbon fibers, whereas the flexural strength improved significantly. However, the flexural strength diminished by adding carbon fibers above to critical value (5 vol%) due to residual thermal stresses, nonhomogeneous structure and graphitization of carbon fibers. It was found that the composite with 5 vol% C_f had the highest flexural strength (482 MPa), which was enhanced by 20% compared with the TiB₂–SiC composite.     

A Strong and Damage-Tolerant Oxide Laminate

A novel laminar oxide composite was developed. This oxide laminate, which was fabricated by hot pressing, consisted of three types of layers, which were stacked in a repeating sequence of YPO4, yttria-stabilized ZrO₂, 30 vol% yttria-stabilized ZrO₂-70 vol% Al₂O₃, and yttria-stabilized ZrO₂. The behavior of the oxide laminate was evaluated by four-point flexural testing and the indentation technique. The flexural strength from one test was 358 MPa, and the load-displacement curve of this test displayed a graceful failure. Pronounced interfacial delamination contributed to a high work of fracture and damage tolerance. These properties have rarely been observed in oxide composites and are comparable to those of non-oxide composites, such as SiC/graphite, SiC/BN, and Si₃N₄/BN laminates.     

低压化学气相渗透法制备2.5维SiCf/SiC复合材料

采用低压化学气相渗透法制备了具有和不具有热解炭界面层的2.5维连续SiC纤维增强的SiC复合材料(SiCf/SiC).SiC纤维的体积分数为30%和41%.所制备复合材料的气孔率为20%左右.当纤维为30%时,沉积有0.1 μm热解炭界面层的复合材料的弯曲强度由未加热解炭界面层的232MPa增加到328MPa,而且材料由灾难性断裂转变为非灾难性断裂.在同一制备条件下,纤维体积分数为41%的SiCf/SiC比30%的SiCf/SiC具有更高的气孔率.纤维为41%时,热解炭界面层厚度为0.1 μm的SiCf/SiC的弯曲强度只有244MPa,但是它具有更高的韧性和更长的纤维拔出长度.     

Optimisation of the spark plasma sintering process for high volume fraction SiCp/Al composites by orthogonal experimental design

Based on orthogonal experimental design (OED), the effects of the sintering pressure, sintering temperature and holding time on the mechanical properties of 50 vol% silicon carbide particle (SiCp)/2024Al composites prepared by spark plasma sintering (SPS) were investigated. The sintering pressure had the greatest effect on the density and bending strength of the material among these three factors, followed by sintering temperature and holding time. The optimised process conditions for producing the 50 vol% SiCp/2024Al were sintering at 550 °C for 5 min under 40 MPa, which resulted in a composite material with a density of 99.7% and good interface bonding with a comparatively high bending strength of 766.65 MPa. This work provides a promising method to produce high volume fraction composites that can meet high strength requirements.     

三维针刺C/SiC复合材料的结构特征和力学性能

采用化学气相渗透法制备了在厚度方向上具有纤维增强的三维针刺碳纤维增强碳化硅(C/SiC)陶瓷基复合材料,复合材料的密度和气孔率分别为2.15 h/cm3和16%.三维针刺C/SiC复合材料中的针刺纤维将各层紧密结合在一起,其层间抗剪切强度显著提高,为95MPa,比二维碳布叠层C/SiC复合材料的剪切强度(35MPa)高171.4%.三维针刺C/SiC复合材料的拉伸强度和弯曲强度分别为159MPa和350MPa,断裂模式为非脆性断裂,包括:裂纹扩展、偏转,碳纤维的拉伸断裂和逐步拔出.     

Joining of sintered SiC ceramics at a lower temperature using borosilicate glass with laser cladding Si modification layer

The silicon carbide whose surface had been modified by laser cladding silicon layer was soldered by borosilicate glass. And the borosilicate glass solder had a thermal expansion coefficient similar to that of the silicon carbide substrate. The laser cladding silicon layer significantly improved the wettability between molten glass solder and silicon carbide and could reduce the soldering temperature. A sandwich-like joining structure (SiC/Si/solder/Si/SiC) was made after the borosilicate glass slurry put on the laser cladding silicon layers. The microstructure, compositions, and interfacial properties were studied. Results showed that good adhesion between silicon carbide and the glass soldering layer was achieved. The flexural strength of the connection structure prepared at 900 °C in the air reached 110 MPa. This research provides an effective technical solution for realizing local heat treatment soldering of large silicon carbide components.     

SiC纳米线增强反应烧结碳化硅陶瓷的性能研究

以单晶SiC纳米线作为增强体,碳化硅-碳为陶瓷基体,在1550℃下,采用反应烧结制备碳化硅基陶瓷复合材料(SiCnf/SiC).结合X射线衍射、万能试验机和扫描电镜等检测和分析,研究SiC纳米线对复合材料的微结构和力学性能的影响.研究表明:与未加入SiC纳米线的反应烧结碳化硅陶瓷相比,添加SiC纳米线的复合陶瓷的抗弯强度和断裂韧性都得到显著的提高,抗弯强度提高了52％,达到320 MPa(SiC纳米线含量为12wt％),断裂韧性提高了40.6％,达到4.5 MPa· m1/2(SiC纳米线含量为15wt％);反应后的SiC纳米线仍然可以保持原有的竹节状结构,且随着SiC纳米线的加入,复合陶瓷的断口可以观察到SiC纳米线拔出现象.但由于SiC纳米线“架桥”的现象,添加过量的纳米线会降低复合陶瓷的密度和限制复合陶瓷力学性能的提高.同时还讨论了SiCnf/SiC的增强机理.     

High-frequency welding of polypropylene using dielectric ceramic compounds in composite adhesive layers

In this study, high-frequency welding of polypropylene by melting composite adhesive layers containing dielectric ceramics was investigated. Various dielectric ceramics were mixed in a fixed ratio with polypropylene to make the composite adhesive layers, and the resulting dielectric properties were measured using an impedance analyser. The highest loss factor in the composite adhesive layer was found when 40 vol% silicon carbide (SiC) was used in the mixture. Dynamic viscoelasticity measurements showed that all composite adhesive layers softened at approximately 170 °C and melted (fluidised) at approximately 190 °C. Each composite adhesive layer was inserted between two polypropylene plates, and irradiated at a frequency of 40 MHz. The composite adhesive layers that included 20 vol% anatase-titanium oxide, 20 vol% or 40 vol% zinc oxide and 20 vol% or 40 vol% SiC melted in 40–70 s. The bond strength of the welded material obtained was high, and the adherend failure occurred by a tensile lap shear test. The heating efficiencies of the composite adhesive layers by high-frequency radiation were related to the tanδ/ε′ value of the composites.     

氧化铝料浆预浸料结合PIP工艺制备SiC/Al2O3-SiC陶瓷基复合材料及性能研究

连续碳化硅纤维增强碳化硅陶瓷基复合材料（SiC/SiC）具有低密度、耐高温、低氚渗透率和优异的辐照稳定性的优点，在航空、航天、核能等领域具有广泛的应用前景。本文针对PIP工艺制备SiC/SiC复合材料周期长、孔隙率较高及易氧化的问题，通过料浆预浸料工艺在基体中引入氧化铝陶瓷形成SiC/Al2O3-SiC复相基体复合材料，并对复合材料制备工艺过程、微观形貌及力学性能进行系统表征。分析结果表明，SiC/Al2O3-SiC复相基体复合材料制备周期较传统PIP工艺大幅度缩短，且复合材料孔隙率明显降低，从11.6%左右降低至6%，拉伸强度为316.5MPa，提升了12.3%，弯曲强度与SiC/SiC相当，但层间剪切强度较低，仅为16.3MPa，有待进一步提高。     

MCMB–SiC composites; new class high-temperature structural materials for aerospace applications

Graphite–silicon carbide (G–SiC), carbon/carbon–silicon carbide (C/C–SiC) and mesocarbon microbeads–silicon carbide (MCMB–SiC) composites were produced using liquid silicon infiltration (LSI) method and their physical and mechanical properties, including density, porosity, flexural strength and ablation resistance were investigated. In comparison with G–SiC and C/C–SiC composites, MCMB–SiC composites have the highest bending strength (210 MPa) and ablation resistance (9.1%). Moreover, scanning electron microscopy (SEM) and optical microscopy (OM) are used to analyze the reacted microstructure, pore morphology and pore distribution of carbon-based matrices. As a result, SiC network reinforcement was formed in situ via a reaction between liquid silicon and carbon. The unreacted carbon and solidified silicon are two phases present in the final microstructure and are characterized by X-ray diffraction (XRD). Based on the results obtained and the low-cost processing of pitch-based materials, the MCMB–SiC composite is a promising candidate for aerospace applications.     

Gelcasting of silicon carbide ceramics using phenolic resin and furfuryl alcohol as the gel former

A new non-aqueous gelcasting system of phenolic resin and furfuryl alcohol combined with a curing catalyst was developed for casting of reaction bonded silicon carbide ceramics. This gelling system could be carried out in air, and the surface exfoliation phenomenon that seems inherent to the acrylamide gelcasting system could also be eliminated. Polymerization of the premix solutions and rheological properties of the non-aqueous silicon carbide suspensions were studied. After curing and subsequent pyrolysis of the concentrated silicon carbide suspension, homogenous silicon carbide/carbon green body with a relatively high strength of about 18 MPa could be formed. Dense complex-shaped SiC ceramic parts with flexure strength of 300±20 MPa and fracture toughness of 3.87±0.19 MPa m^1/2 can be successfully produced after reaction sintering at 1700 °C for 30 min under vacuum.     

Low-temperature joining of SiC ceramics using NITE phase with Al2O3-Ho2O3 additive

In order to avoid the property degradation resulting from high-temperature joining process, nano-infiltrated transient eutectoid (NITE) phase with the Al₂O₃-Ho₂O₃ as the joining adhesives was adopted to join silicon carbide (SiC) ceramics with the attempts to lower down the joining temperature. The liquid-phase-sintered silicon carbide (LPS-SiC) specimens were joined at 1500-1800°C by spark plasma sintering (SPS) under the pressure of 20 MPa. The results of the shear test and microstructure observation showed that the joining process could be finished at a relatively lower temperature (1700°C) compared to other NITE-phase joining. In contrast to the shear strength of 186.4 MPa derived from the SiC substrate, the joint exhibited the shear strength of 157.8 MPa with the fully densified interlayer.     

Co-reinforcing of ZrB2–SiC ceramics with optimized ZrC to Cf ratio

Characteristics of ZrB₂–SiC ultrahigh temperature ceramic matrix composites (UHTCMCs) reinforced with ZrC and carbon fiber (C_f) were investigated in this article. Spark plasma sintering (SPS) process was utilized to fabricate the samples at 1800 °C for 5 min under 30 MPa punch pressure and vacuumed atmosphere. In all samples, the volume ratio of ZrB₂: SiC was equal to 4:1, and the summation of ZrC and C_f reinforcements was 7.5 vol% with different ZrC: C_f ratios. Field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), densitometry, flexural strength, and hardness measurements were employed for characterization of the prepared samples. Microstructural inspection revealed the formation of SiC sheath around the carbon fibers due to several reactions in the surface SiO₂ layers existed on the SiC particles. Optimal flexural strength (628.4 MPa) and hardness (20.8 GPa) values were achieved for the sample co-reinforced with 6.5 vol% ZrC and 1 vol% C_f, with a relative density of 97.7%.     

Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration

Complex silicon carbide (SiC) ceramic components are difficult to fabricate due to their strong covalent bonds. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components. This study tried to obtain low silicon content silicon carbide ceramics by binder jetting followed by phenolic resin impregnation and pyrolysis (PRIP) and liquid silicon infiltration (LSI). BJ was used for the SiC green parts fabrication, and the highest compressive strength (7.7 ± 0.3 MPa) and lowest dimensional deviations (1.2–1.6 mm) were obtained with the printing layer thickness of 0.15 mm. Subsequently, PRIP treatments were introduced to increase the carbon content for the following LSI process. As the number of PRIP cycles increased, the carbon density of SiC/C preform increased and the porosity decreased. After the LSI treatment, the final Si-SiC composites processed with 2 PIRP cycles reached the highest flexural strength (257 ± 14.26 MPa) and the best wear resistance. This was attributed to the low residual silicon content (10.2 vol%) and almost no residual carbon. Furthermore, several complex structural components were fabricated using these methods. The preparation of complex components verifies the feasibility of BJ and LSI for manufacturing high-strength and high-precision SiC ceramics. Besides, this work hopes to provide technical guidance for the preparation of complex SiC composites in the future.     

Combined role of SiC particles and SiC whiskers on the characteristics of spark plasma sintered ZrB2 ceramics

In this research work, the effects of silicon carbide (SiC) as the most important reinforcement phase on the densification percentage and mechanical characteristics of zirconium diboride (ZrB₂)-matrix composites were studied. In this way, a monolithic ZrB₂ ceramic (as the baseline) and three ZrB₂ matrix specimens each of which contains 25 vol% SiC as reinforcement in various morphologies (SiC particulates, SiC whiskers, and a mixture of SiC particulates/SiC whiskers), have been processed through spark plasma sintering (SPS) technology. The sintering parameters were 1900 °C as sintering temperature, 7 min as the dwell time, and 40 MPa as external pressure in vacuum conditions. After spark plasma sintering, a relative density of ~96% was obtained (using the Archimedes principles and mixture rule for evaluation of relative density) for the unreinforced ZrB₂ specimen, but the porosity of composites containing SiC approached zero. Also, the assessment of sintered materials mechanical properties has shown that the existence of silicon carbide in ZrB₂ matrix ceramics results in fracture toughness and microhardness improvement, compared to those measured for the monolithic one. The simultaneous addition of silicon carbide particulates (SiC_p) and whiskers (SiC_w) showed a synergistic effect on the enhancement of mechanical performance of ZrB₂-based composites.     

Mechanical Characterization of Annealed ZrB2–SiC Composites

Composites consisting of 70 vol% ZrB₂ and 30 vol% α‐SiC particles were hot pressed to near full density and subsequently annealed at temperatures ranging from 1000°C to 2000°C. Strength, elastic modulus, and hardness were measured for as‐processed and annealed composites. Raman spectroscopy was employed to measure the thermal residual stresses within the silicon carbide (SiC) phase of the composites. Elastic modulus and hardness were unaffected by annealing conditions. Strength was not affected by annealing at 1400°C or above; however, strength increased for samples annealed below 1400°C. Annealing under uniaxial pressure was found to be more effective than annealing without applied pressure. The average strength of materials annealed at 1400°C or above was ~700 MPa, whereas that of materials annealed at 1000°C, under a 100 MPa applied pressure, averaged ~910 MPa. Raman stress measurements revealed that the distribution of stresses in the composites was altered for samples annealed below 1400°C resulting in increased strength.     

Improvement of toughness of reaction bonded silicon carbide composites reinforced by surface-modified SiC whiskers

To improve the reliability, especially the toughness, of the reaction bonded silicon carbide (RBSC) ceramics, silicon carbide whiskers coated with pyrolytic carbon layer (PyC-SiC_w) by chemical vapor deposition (CVD) were introduced into the RBSC ceramics to fabricate the SiC_w/RBSC composites in this study. The microstructures and properties of the PyC-SiC_w/RBSC composites under different mass fraction of nano carbon black and PyC-SiC_w were investigated methodically. As a result, a bending strength of 550 MPa was achieved for the composites with 25 wt% nano carbon black, and the residual silicon decreased to 11.01 vol% from 26.58 vol% compared with the composite of 15 vol% nano carbon black. The fracture toughness of the composites reinforced with 10 wt% PyC-SiC_w, reached a high value of 5.28 MPa m^1/2, which increased by 39% compared to the RBSC composites with 10 wt% SiC_w. The residual Si in the composites deceased below to 7 vol%, resulting from the combined actively reaction of nano carbon black and PyC with more Si. SEM and TEM results illustrated that the SiC_w were protected by PyC coating. A thin SiC layer formed of outer surface of whiskers can provide a suitable whisker-matrix interface, which is in favor of crack deflection, SiC_w bridging and pullout to improve the bending strength and toughness of the SiC_w/RBSC composites.     

Synthesis of monolithic SiC aerogels with high mechanical strength and low thermal conductivity

The monolithic silicon carbide (SiC) aerogels were converted from catechol-formaldehyde/silicon composite (CF/SiO₂) aerogels through carbothermal reduction and calcination. In the process of preparing the CF/SiO₂ aerogel, a new method was proposed to produce more silicon carbide and enhanced the mechanical properties of the SiC aerogel. This method was realized by adding an alkaline silica sol as supplemental silicon source. The principle process of CF/SiO₂ aerogels converting to SiC aerogels was discussed based on experiment and results analysis, while the microstructure, mechanical properties, and thermal properties of the prepared SiC aerogels were investigated. The results show that the as-synthesized SiC aerogels consist of β-SiC and a small amount of α-SiC nanocrystalline. It possessed a mesoporous structure and a low thermal conductivity 0.049 W/(m∙K), a relatively high compressive strength 1.32 MPa, and a relatively high specific surface area 162 m²/g. Due to their outstanding thermal and mechanical properties, the prepared SiC aerogels present potential applications in thermal insulation field, such as space shuttles and aerospace carrier thermal protection materials.     

New Approach for Macro Porous RB‐SiC Derived from SiC/Novolac‐type Phenolic Composite

A novel fabrication route to make macroporous silicon carbide (SiC) has been proposed in this study. The route is composed of the following two steps: the fabrication of porous α‐SiC/novolac‐type phenolic composite using hexamethylenetetramine (HMT) as a curing/blowing agent for the novolac monomer and a conventional reaction‐bonded (RB) sintering of the composite. The α‐SiC/novolac‐type phenolic composite was carbonized at 800°C for 2 h in N₂ gas and then reacted with the molten silicon at 1450°C for 30 min under vacuum, resulting in the macroporous RB‐SiC with an open porosity of 48% and relatively large pore size of ~110 μm. The compressive strength of the macroporous RB‐SiC was 113 MPa, which is relatively high compared to those reported for macroporous SiC of equivalent porosities and pore sizes.