Mullite (Nextel™ 720) fibre-reinforced mullite matrix composites exhibiting favourable thermomechanical properties

A mullite matrix containing homogeneously distributed ultra-fine (70–350 nm) pores was reinforced with NdPO₄-coated woven mullite fibre mats (Nextel™ 720) leading to damage-tolerant composites with good high temperature (1300 °C) strength and thermal cycling resistance. Electrophoretically deposited fibre preforms were placed in a high-load pressure filtration assembly, leading to formation of consolidated compacts with high green densities. After sintering at 1200 °C for 3 h, the compacts had a density of 86.4% of theoretical density and showed damage-tolerant behaviour up to 1300 °C, with flexural strength values of 235 MPa and 224 MPa at room temperature and 1300 °C, respectively. No significant microstructural damage was detected after thermal cycling the samples between room temperature and 1150 °C for up to 300 cycles. The thermomechanical test results combined with detailed electron microscopy observations indicate that the overall composite behaviour in terms of damage-tolerance, thermal capability and thermal cycling resistance is mainly controlled by two microstructural features: (1) the presence of a dense NdPO₄ interphase but weak bonding with the matrix or fibre and (2) the presence of homogeneously distributed nano pores (<350 nm) within the mullite matrix.     

Aluminosilicate fiber/mullite matrix composites with favorable high-temperature properties

Oxide-based ceramic matrix composites with a highly porous mullite matrix and Nextel™ 720 alumino silicate fibers have been fabricated by infiltrating filaments with a mullite precursor slurry, and by subsequent one-dimensional (1D) and two-dimensional (2D)-winding up the fiber bundles on mandrels. The green bodies were pressureless sintered in air at 1300°C. These composites which require no fiber/matrix interface are characterized by favorable damage tolerance and bending strengths of 160 MPa at room temperature and up to temperatures of 1200°C. These properties make it an excellent low-cost choice for combustion chamber liners, diffusor rings and other thermal protection systems for high temperature applications in oxidizing environment.     

Fabrication technologies for oxide–oxide ceramic matrix composites based on electrophoretic deposition

Electrophoretic deposition (EPD) was used to fabricate alumina matrix composites with high volume fraction of woven fibre mat (Nextel™ 720) reinforcement in a multilayer structure. Colloidal suspensions of Al₂O₃ nanoparticles in ethanol medium with addition of 4-hydrobezoic acid were used for EPD. Two different techniques were developed for fabrication of Al₂O₃ matrix/Nextel™ 720 fibre composites. The first method is a combination of standard EPD of single fibre mats with a subsequent lamination procedure to fabricate the multilayered composite. The second method involves the simultaneous infiltration of several (three or more) Nextel™ 720 fibre mats by EPD in a tailor-made cell. The composites exhibit a homogeneous matrix microstructure, characterised by a very high particle packing density and relatively low porosity after sintering at 1300 °C. The EPD cell allows production of relatively large bodies (10 cm diameter). By combination of the multilayer EPD infiltration and lamination processes developed here, thick ceramic matrix composite components (>10 mm thickness) can be fabricated, which opens the possibility of greater industrial application of the materials.     

Damage tolerant oxide/oxide fiber laminate composites

Oxide-fiber/oxide-matrix composites were developed using non-infiltrated woven fiber layers between matrix-infiltrated fiber layers in order to achieve damage tolerant behavior. A fiber interface coating was not used. This technique enables damage tolerance in materials with strong fiber-matrix bonding and under oxidizing conditions. Fabrication of composites was carried out through a slurry infiltration technique. Slurries for fiber (Nextel™ 720, 3M) infiltration were prepared using a submicron α-Al₂O₃ powder coated with an amorphous SiO₂-layer through a sol–gel process. Hot-pressing was used to densify and bond the laminate layers together, followed by pressureless heat-treatment to allow mullite to form. Room temperature three-point bending tests were performed on as-received samples and on samples which underwent long-term annealing at high temperatures (1200–1300°C) in air. Subsequent examination revealed that due to the lack of a fiber interface coating, matrix-infiltrated fiber layers behaved in a quasi-monolithic manner with little or no crack deflection. Layers of non-infiltrated fibers, however, provided damage tolerance by deflecting cracks in the plane of the laminate and by serving as a mechanical bond between matrix-infiltrated layers. The laminate composites demonstrate reasonable room-temperature fracture strength both in the as-received state (88 MPa) and after exposure to 1300°C air for 200 h (72 MPa) along with extensive fracture deflection through the layers of non-infiltrated fiber. Composite properties, specifically fracture strength and damage tolerance, can be tailored by varying lay-up and processing parameters such as fiber-matrix ratio and type of fiber weave.     

Microstructural evolution under load and high temperature deformation mechanisms of a mullite/alumina fibre

A two-phase mullite alumina fibre, the 3M Nextel 720 fibre, has been studied in tension and creep. The fibre shows the highest creep resistance of all current commercial fine oxide fibres up to 1500 °C. The creep mechanisms involve progressive dissolution of mullite and simultaneous reprecipitation of alumina into elongated oriented grains and grain boundary sliding by a thin alumino-silicate liquid phase. The rate of grain growth in creep at a given temperature is dependant on the applied stress. The combination of sub-micron size mullite crystallites and alumina grains gives rise to a high sensitivity to alkaline contamination. Stress enhanced diffusion of the contaminants from the fibre surface results in crack nucleation, dissolution of mullite, formation of a liquid phase and slow crack growth. From 1200 °C, this process is coupled with a fast α-alumina grain growth at the fibre surface.     

Development and characterisation of high-density oxide fibre-reinforced oxide ceramic matrix composites with improved mechanical properties

A low cost and reliable ceramic matrix composite fabrication route has been developed. It involves the coating of 2D woven ceramic fibres (Nextel? 720) with oxide nano-size ceramic particles by electrophoretic deposition (EPD) followed by impregnation of the coated fibres with ceramic matrix and warm pressing at 180 °C to produce the “green” component ready for pressureless sintering. The effects of two different weak interface materials, NdPO₄ and ZrO₂, on the thermomechanical properties of the composites are also examined. Damage mechanisms, such as debonding, fibre fracture, delamination and matrix cracking within the composite plates subjected to tensile loading are analysed using acoustic emission technique and correlated with microstructure. It is shown that the composites with NdPO₄ interface, 10% porosity and 40 vol.% fibre loading have superior themomechanical properties in terms of strength and damage-tolerant behaviour in multilayer plate form. The improved sinterability and microstructure stability at moderate temperatures ensure both the fibre integrity and load transfer efficiency resulting in high strength damage-tolerant composites. The final components produced are considered to be suitable for use as shroud seals and insulating plates for combustor chambers in aircraft engines.     

Mechanical characterisation of mullite-based ceramic matrix composites at test temperatures up to 1200°C

Nextel 610 fibre-reinforced mullite-based matrix fabricated by Dornier Forschung was characterised at DLR Institute of Materials Research. The material was produced by the polymer route after coating the fibres with a 0.1 μm thick carbon layer. The composite was manufactured by infiltrating the fibres with a slurry containing a diluted polymer and mullite powder, curing in an autoclave and subsequently heat treating and pyrolysis of the polymer. A final heat treatment in air is performed to remove the carbon coating and to reduce the residual stresses. A (0/90/0/90/0/90)_s-laminate was produced with an average fibre volume fraction of 45.6% and a porosity of 15.9%. Dog-bone-type tensile specimens with a width of 10 mm were cut from the plate by water jet and tested at temperatures up to 1200°C in air. The tensile strength at room temperature measured 177.4 MPa and linearly decreased to 145.2 MPa at a temperature of 800°C. A stronger decrease occurred at 1000 and 1200°C. In contradiction to ceramic matrix composites manufactured by the CVI-route the stress–strain behaviour is nearly linear up to failure. The modulus of the composite (at room temperature 108.8 GPa) is analysed on the basis of the expected moduli of the fibres and the mullite matrix. It can be concluded that the contribution of the matrix to the modulus of the composite is low, caused by porosity and components other than mullite. The intralaminar shear strength at room temperature measured 36 MPa. This value reflecting shear transfer capability of fibre to matrix limits the amount of fibre pull-out.     

Joining and testing of alumina fibre reinforced YAG-ZrO2 matrix composites

Alumina (Nextel? 610) fibre reinforced YAG-ZrO₂ matrix composites were successfully joined by using different brazing alloys, metallic interlayers and a glass-ceramic. All joints were mechanically stable and free of cracks. Three commercial brazing alloys and a new alloy based on Ti/Cu/Al interlayers were selected to join these composites for applications in a non-oxidizing environment. A glass-ceramic based on SiO₂-Al₂O₃-CaO-MgO was developed in case the joined component needs to be oxidation resistant. To evaluate the thermal stability, all joined composites were aged up to 100 h in air at 550 °C for brazing joints or 850 °C and 930 °C for glass-ceramic joints. The mechanical strength was measured using single lap and four point bending tests before and after ageing. Four point bending tests on glass-ceramic joined samples showed an average joint strength of about 70 MPa which is 35% of as-received composites.     

Microstructural and mechanical characterization of a mullite fiber

The effect of thermal exposure on a mullite fiber was analyzed. This type of mullite fiber, consisting of γ-Al₂O₃ and amorphous SiO₂, was developed for high-temperature applications. Heat treatments at temperatures ranging from 900 °C to 1500 °C for 1h were performed in air. Investigations showed that the tensile strength of the initial fiber was about 1.60 GPa. And the elastic modulus was about 133.51 GPa. The bundles’ strength decreased at 900 °C slightly after thermal treatment, then increased and got a maximum at 1100 °C with 1.65 GPa. At above 1100 °C, the strength degraded sharply due to the mullite phase transformation and the exaggerated grain growth. At 1300 °C, the phase reaction almost finished with a tensile strength of 0.86 GPa. And the strength retention was only 47.50%. When the heat-treated temperature got to 1500 °C, the density of surface defects in the fiber surged, making it too fragile and weak to go through the tensile tests.     

On the mechanical,thermophysical and dielectric properties of Nextel™ 440 fiber reinforced nitride matrix (N440/Nitride) composites

The Nextel? 440 fiber reinforced nitride matrix (N440/Nitride) composites were fabricated by precursor infiltration and pyrolysis (PIP) route. The results demonstrated that the original N440 fiber had a phase composition of amorphous SiO₂ and γ-Al₂O₃. Its single filament tensile strength was 3.03 GPa (at room temperature), while it dropped to 72.6% and 35.1% at 1200 °C and 1400 °C, respectively. The phase content of N440/Ntride composites was mainly γ-Al₂O₃ and amorphous BN, as well as mullite phase (formed at > 1100 °C). The composites owned a flexural strength up to 76.0 MPa at room temperature. The stair-stepping decrease in the load-displacement curve and fiber pull-outs in the fracture surface indicated a good fiber/matrix interface and toughness. By heating at 1400 °C, the composites still possessed 67.4% of original bending strength. It was found that the high temperatures caused strong fiber-matrix bonding and severe fiber degradation. The specific heat, CTE and thermal conductivity of the composites were 0.325–0.586 J g^?1 K^?1, (3.2–4.0) × 10^?6 K^?1 and 0.78–3.47 W m^?1 K^?1, respectively. The composites possessed a dielectric constant of 4.25–4.35 and loss tangent of 0.004–0.01 at 8–12 GHz. The good overall performances enabled the N440/Nitride composites advanced high-temperature wave-transparent applications.     

Microstructure evolution and mechanical behavior of a mullite fiber heat-treated from 1100 to 1300°C

In this paper, the effect of phase transformation on microstructure evolution and mechanical behaviors of mullite fibers was well investigated from 1100 to 1300°C. In such a narrow temperature range, the microstructure and mechanical properties showed great changes, which were significant to be studied. The temperature of the alumina phase transformation started at below 1100°C. The main phases in fibers were γ-Al₂O₃ and δ-Al₂O₃ with amorphous SiO₂ at 1150°C. The stable α-Al₂O₃ formed at 1200°C. Then the mullite phase reaction occurred. As the alumina phase reaction took place, the tensile strength increased with the increasing temperature. In particular, the filaments achieved the highest strength at 1150°C with 1.98 ± 0.17 GPa, and the Young's modulus was 163.08 ± 4.69 GPa, showing excellent mechanical performance. After 1200°C, the mullite phase reaction went on with the crystallization of orthorhombic mullite. The density of surface defects increased rapidly due to thermal grooving, which led to mechanical properties degrade sharply. The strength at 1200°C was 1.01 ± 0.15 GPa with a strength retention of 63.13%, and the Young's modulus was 184.14 ± 10.36 GPa. While at 1300°C, the tensile strength was 0.64 ± 0.14 GPa with a strength retention of only 40.00%.     

High-temperature mechanical properties of NextelTM 610 fiber reinforced silica matrix composites

Novel Nextel? 610 fiber reinforced silica (N610f/SiO₂) composites were fabricated via sol-gel process at a sintering temperature range of 800–1200?°C. The sintering-temperature dependent microstructures and mechanical properties of the N610f/SiO₂ composites were investigated comprehensively by X-ray diffraction, nanoindentation, three-point bending etc. The results suggested a thermally stable Nextel? 610 fiber whose properties were barely degraded after the harsh sol-gel process. A phase transition in the silica matrix was observed at a critical sintering temperature of 1200?°C, which led to a significant increase in the Young's modulus and hardness. Due to the weak fiber/matrix interfacial interaction, the 800?°C and 1000?°C fabricated N610f/SiO₂ composites exhibited quasi-ductile fracture behaviors. Specially, the latter possessed the highest flexural strength of ≈ 164.5?MPa among current SiO₂-matrix composites reinforced by fibers. The higher sintering-temperature at 1200?°C intensified the SiO₂ matrix, but strengthened the interface, thus resulting in a brittle fracture behavior of the N610f/SiO₂ composite. Finally, the mechanical properties of this novel composite presented good thermal stability at high temperatures up to 1000?°C.     

Single crystalline mullite fibres obtained by the internal crystallisation method: Microstructure and creep resistance

Single crystalline mullite fibres, which are expected to be an excellent reinforcement for high temperature composite materials, can be produced by using the internal crystallisation method. The present paper sheds light to mechanisms of crystallisation of mullite fibres under conditions of the internal crystallisation method, which is actually crystallisation of a melt in the continuous channels of a molybdenum carcass. Mullite occurs to appear close to 2:1 composition independent of the composition of the melt. Inclusions of a silica-based glassy phase are also present on the periphery of a fibre. The glassy phase yields a decrease in the creep resistance of mullite fibres at temperatures above 1500 °C. Still, the fibres obtained from the raw material with the Al₂O₃/SiO₂ molar ratio of 2.05 have excellent creep resistance at a temperature of 1400 °C and fairly high creep resistance at 1500 °C.     

Polymer-derived mullite–SiC-based nanocomposites

Ceramic mullite–SiC nanocomposites were successfully produced at temperatures below 1500 °C by the polymer pyrolysis technique. An alumina-filled poly(methylsilsesquioxane) compound was prepared by mechanically mixing and cross-linking via a catalyst prior to pyrolysis. Heat treatment of warm pressed alumina/polymer bulk samples under the exclusion of oxygen (inert argon atmosphere) up to 1500 °C initiated crystallization of mullite even at pyrolysis temperatures as low as 1300 °C. The influence of the filler and of the pyrolysis temperature on the crystallization behavior of the materials has been investigated. Based on thermal analysis in combination with elemental analysis and X-ray powder diffraction studies four polymer mixtures differing in type and content of nano-alumina powders were examined. Nano-sized γ-Al₂O₃ powders functionalized at the surface by octylsilane groups proved to be more reactive towards the preceramic polymer leading to the formation of a larger weight fraction of mullite crystals at lower processing temperatures (1300 °C) as compared to native nano-γ-Al₂O₃ filler. Moreover, the functionalized nano-alumina particles offer an enhanced homogeneity of the distribution of alumina nano-particles in the starting polysiloxane system. In consequence, the received ceramic samples exhibited a nano-microstructure consisting of crystals of mullite with an average dimension in the range of 60–160 nm and silicon carbide crystals in the range of 1–8 nm.     

Corrosion degradation of mullite subject to carbon monoxide atmosphere at 1000oC–1600°C

Thus far, studies on the damage to refractory materials under carbon monoxide atmospheres have mostly concentrated on the effects of carbon deposition, and the testing temperature was always set at approximately 500°C to promote the deposition of carbon. However, this testing temperature is far below the operating temperature of most refractories. In this study, mullite, a widely used high-temperature structural material, was subjected to a carbon monoxide atmosphere at 1000°C-1600°C to investigate its phase and microstructural evolutions. Changes to the grain boundaries were initially observed in mullite specimens treated at 1000°C and 1200°C. After treatment at 1400°C, the specimen surface comprised α-Al₂O₃, a glass phase, and a small amount of mullite. However, treatment at 1600°C resulted in only α-Al₂O₃ and a small amount of glass phase on the surface. Additionally, pores and voids were found in the glass phase on the surface and in the bulk of the specimens treated at 1400°C and 1600°C. This study demonstrated the stability of pure mullite in a carbon monoxide atmosphere and revealed that impurities accelerating generation of the liquid phase in Al₂O₃–SiO₂ system significantly affect the stability of mullite in a carbon monoxide atmosphere.     

Effects of sintering temperature on mechanical properties of 3D mullite fiber (ALF FB3) reinforced mullite composites

A new method to weaken the interfacial bonding and increase the strength of 3D mullite fiber reinforced mullite matrix (Mu_f/Mu) composites is proposed and tested in this paper. Firstly, Mu_f/Mu composites were fabricated through sol–gel process with varied sintering temperature. Then, the effects of sintering temperature on mechanical properties of the composites were tested. As sintering temperature was raised from 1000 °C to 1300 °C, the three-point flexural strength of the composites firstly decreased from 66.17 MPa to 41.83 MPa, and then increased to 63.17 MPa. In order to explain the relationship between composite strength and sintering temperature, morphology and structure of the mullite fibers and mullite matrix after the same heat-treatment as in the fabrication conditions of the composites were also investigated. Finally, it is concluded that this strength variation results from the combined effects of matrix densification, interfacial bonding and fiber degradation under different sintering temperatures.     

Evolution of the structure and mechanical performance of Cansas-II SiC fibres after thermal treatment

Herein, an in-depth analysis of the effect of heat treatment at temperatures between 900 and 1500 °C under an Ar atmosphere on the structure as well as strength of Cansas-II SiC fibres was presented. The untreated fibres are composed of β-SiC grains, free carbon layers, as well as a small amount of an amorphous SiC_xO_y phase. As the heat-treatment temperature was increased to 1400 °C, a significant growth of the β-SiC grains and free carbon layers occurred along with the decomposition of the SiC_xO_y phase. Moreover, owing to the decomposition of the SiC_xO_y phase, some nanopores formed on the fibre surface upon heating at 1500 °C. The mean strength of the Cansas-II fibres decreased progressively from 2.78 to 1.20 GPa with an increase in the heat-treatment temperature. The degradation of the fibre strength can be attributed to the growth of critical defects, β-SiC grains, as well as the residual tensile stress.     

界面类型对三维Nextel 720纤维增韧莫来石陶瓷基复合材料力学性能的影响

采用化学气相渗透工艺在Nextel 720纤维表面制备PyC和PyC／SiC两种涂层，然后以正硅酸乙酯和异丙醇铝作为先驱体，以先驱体浸渗热解法制备三维Nextd 720纤维增韧莫来石陶瓷基复合材料，比较分析了两种涂层复合材料的力学性能和断裂模式。结果表明：具预先涂覆PyC的复合材料中纤维与基体直接接触，发生烧结形成强结合界面，复合材料脆性断裂，三点抗弯强度仅56MPa。PyC／SiC涂层则演化为间隙／SiC复合界面层，SiC成为阻滞纤维与基体接触的阻挡层，间隙保证了纤维拔出，复合材料韧性断裂且三点抗弯强度高达267．2MPa。     

Enhancing thermal stability of oxide ceramic matrix composites via matrix doping

To overcome the main limitation of oxide ceramic matrix composites (Ox-CMCs) regarding thermal degradation, the use of matrix doping is analyzed. Minicomposites containing Nextel 610 fibers and alumina matrices with and without MgO doping were produced. The thermal stability of the minicomposites was evaluated considering their microstructure and mechanical behavior before and after thermal exposures to 1300 °C and 1400 °C for 2 h. Before heat treatment, both composite types showed very similar microstructure and tensile strength. After heat treatment, densification, grain growth and strength loss are observed. Furthermore, the MgO dopant from the matrix diffuses into the fibers. As a result, abnormal fiber grain growth is partially suppressed and MgO-doped composites show smaller fiber grains than non-doped composites. This more refined microstructure leads to higher strength retention after the heat treatments. In summary, doping the matrix can increase the overall thermal stability without impairing the room-temperature properties of Ox-CMCs.     

Microstructure and properties of SiCf/SiC composite joints with CaO–Y2O3–Al2O3–SiO2 interlayer

Using CaO, Y₂O₃, Al₂O₃, and SiO₂ micron-powders as raw materials, CaO–Y₂O₃–Al₂O₃–SiO₂ (CYAS) glass was prepared using water cooling method. The coefficient of thermal expansion (CTE) of CYAS glass was found to be 4.3 × 10^?6/K, which was similar to that of SiC_f/SiC composites. The glass transition temperature of CYAS glass was determined to be 723.1 °C. With the increase of temperature, CYAS glass powder exhibited crystallization and sintering behaviors. Below 1300 °C, yttrium disilicate, mullite and cristobalite crystals gradually precipitated out. However, above 1300 °C, the crystals started diminishing, eventually disappearing after heat treatment at 1400 °C. CYAS glass powder was used to join SiC_f/SiC composites. The results showed that the joint gradually densified as brazing temperature increased, while the phase in the interlayer was consistent with that of glass powder heated at the same temperature. The holding time had little effect on phase composition of the joint, while longer holding time was more beneficial to the elimination of residual bubbles in the interlayer and promoted the infiltration of glass solder into SiC_f/SiC composites. The joint brazed at 1400 °C/30 min was dense and defect-free with the highest shear strength of about 57.1 MPa.