Thermal Exposure Effects on the Strength and Microstructure of a Novel Mullite Fiber

The mechanical behavior of the novel fiber CeraFib75 after various thermal exposures is examined. This fully crystalline mullite fiber was developed to exceed the thermal stability of commercially available oxide fibers. Therefore, heat treatments at temperatures ranging from 1000°C to 1400°C for 25 h were performed and results compared to the well‐established Nextel^? 720 fibers. Mechanical characterization was realized with bundle tensile tests using acoustic emission sensors to determinate the fiber failure distributions. Investigations showed that the initial fiber microstructure of mullite grains with traces of alumina transforms starting at 1200°C. Changes include dissociation of the alumina‐rich mullite phase and grain growth. Thus, strength reduction is measured as a result of these microstructure transformations. Remarkably, at 1400°C, fibers become more fragile and Weibull statistics can no longer describe the failure distribution. A relation between the distribution shape and the load redistribution capability of fibers is suggested. This is more pronounced for Nextel^?720 fibers, which present much bigger grains and retain only 10% of their original strength. However, CeraFib75 fibers are more stable and exhibit a strength retention of 50% at the same conditions, which is attributed to the higher amount of mullite phase.     

Insight into the corrosion failure of mullite thermal insulation materials in carbon monoxide

The service condition of mullite thermal insulation materials is complicated, the effects of carbon deposition are always considered the primary cause of damage to mullite ceramic in carbon monoxide atmosphere. In the present study, mullite thermal insulation material was subjected to a carbon monoxide atmosphere at 1100°C–1400°C. The thermodynamics stability, phase composition, and microstructure of the mullite thermal insulation material were analyzed. Furthermore, the effects of carbon monoxide corrosion on thermal shock resistance and compressive creep behavior at high temperatures were evaluated. The carbon content in the mullite-based insulation material is below 0.02% after treatment at 1100°C–1400°C. After treatment at 1400°C, most areas in the specimen comprised corundum and glass phase, and K, Na, Ca, Mg, and Fe were detected as impurities, leading to the improvement of cold crushing strength after 20 thermal shocks but a remarkable recession in high-temperature compressive creep.     

Microstructural Stability and Mechanical Properties of Directionally Solidified Alumina/YAG Eutectic Monofilaments

Fiber strength retention and creep currently limit the use of polycrystalline oxide fibers in ceramic matrix composites making it necessary to develop single crystal fibers. Two-phase alumina/YAG single crystal structures in the form of monofilaments show that the room temperature tensile strength increases according to the inverse square root of the microstructure size. Therefore, microstructure stability will play a significant role in determining the ‘use temperature’ of these fibers along with its creep resistance. In this work, the effects of temperature on microstructural stability and the creep behavior of directionally solidified alumina/YAG eutectic monofilaments were studied. Microstructural stability experiments were conducted in air from 1200 to 1500°C and creep tests at temperatures of 1400 to 1700°C. Inherent microstructure stability was found to be very good, however, extraneous impurity-induced heterogeneous coarsening was significant above 1400°C. The creep strength of monofilaments with aligned microstructures were superior to ones with low aspect ratio morphologies. Mechanisms for microstructural coarsening and creep behavior are discussed.     

Effect of different fiber orientations on compressive creep behavior of siC fiber-reinforced mullite matrix composites

The compressive creep behavior of monolithic mullite and a composite made of mullite reinforced by 40 vol% SiC fiber were investigated at temperatures from 1100 to 1200°C and under stresses from 5 to 55 MPa in air with a loading direction parallel and perpendicular to the fiber direction. For both situations the composite exhibits better creep resistance than monolithic mullite, although there is a creep anisotropy. The improvement in creep resistance when the fibers are parallel to the loading directions is due to the shedding of the applied stress on the SiC fibers, and the improvement in creep resistance when the fibers are perpendicular to the loading direction occurs because the fibers inhibit the lateral deformation of the mullite matrix along the fibers. The improvement mechanisms of the composites were confirmed further by their creep-recovery study, which indicated that the two types of composite specimens exhibit both an apparent creep-recovery behavior on load removal, due to the relaxation of the residual stress state between the mullite matrix and the SiC fibers after unloading. ©     

Control of aluminum phosphate coating on mullite fibers by surface modification with polyethylenimine

Aluminum phosphate (AlPO₄) is a promising oxidation-resistant and weak interface for ceramic-matrix composites. In this research, AlPO₄ coating was deposited on mullite fibers by an improved liquid-phase method based on electrostatic attraction. A cationic polyelectrolyte, polyethylenimine (PEI), was used for surface modification of mullite fibers. The formation process, phase evolution and microstructure of the coating were studied. The zeta potential of AlPO₄ particles, PEI-adsorbed AlPO₄ particles, and PEI-adsorbed mullite particles was characterized to find the proper pH value for improving electrostatic attraction. The obtained AlPO₄ coating was porous and continuous, whose thickness could be controlled by multiple coating cycles. The relatively low calcination temperature (600 or 1000 °C) was a useful heat treatment method to develop bonding between coating and fiber as well as reduce the fiber strength degradation. The phase transformations of AlPO₄ have little volume change, and cristobalite AlPO₄ is thermal compatible with mullite. Therefore, the coating structure was preserved after calcining at 1200 °C. The technique is also applicable for other fibers contained mullite phase to fabricate high-performance AlPO₄ coated mullite/mullite composites.     

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.     

Chemical,phase and structural change of mullite synthesized during sintering of kaolin

Mullite is of great technological relevance but rarely occurs in nature and as a result different approaches have been adopted in its synthesis from alumina bearing minerals. In this study, chemical, phase and structural change of mullite synthesized from sintering of natural kaolinite clay is investigated. Thoroughly beneficiated kaolinite clay powder was obtained from Nigeria and uniaxially pressed into cylindrical compact of 40 × 30 mm followed by sintering at temperatures of 1200°C and 1300°C, respectively. The chemical composition, microstructure change, phase transformation, and reaction bonding were carried out using EDXRF, SEM, XRD, and FT-IR, respectively, to assess the synthesized mullite. The results showed that a well-dispersed primary mullite phase was obtained which was fully developed at increased temperature of 1300°C. Better mullite phase was also obtained with increasing alumina content at more elevated temperature of 1300°C while Si-O-Al bonding of mullite crystals was also obtained from the FT-IR spectra. However, the needle-shaped mullite structure was not achieved which might be attributed to the sintering temperatures 1200°C-1300°C utilized.     

Preparation and characterization of carbon fibers from polyacrylonitrile precursors

The present work deals with the preparation of carbon fibers from polyacrylonitrile (PAN) fibers. The chemical composition and physical properties of the starting fibers were determined. The PAN fibers were stabilized in air at the temperatures (230, 270, and 300°C) with the heating time from 40 to 420 min. The effects of both final stabilization temperature and heating rate on the chemical and physical properties of the prepared stabilized fibers were studied. The chosen stabilized fibers samples were carbonized in argon atmosphere at the temperatures (1000, 1200, and 1400°C) with different heating rates 5, 10, 15, and 20°C min^?1. The effects of both carbonizing temperature and heating rate on the weight loss, density, elemental composition, and IR absorption spectra of carbonized fibers were also studied. The fiber sample, which was carbonized at 1400°C, contains 97.55% carbon, 1.75% nitrogen, and 1.4% hydrogen. This means that carbonizing the stabilized fibers at 1400°C in argon atmosphere is suitable to get oxygen‐free carbon fibers. Therefore, the used carbonizing temperature in the present work (1400°C) is suitable to produce moderate heat‐treated carbon fibers with the heating rate of 15°C min^?1. The modulus of the prepared carbon fibers was compared to that of industrially produced fibers using the results of X‐ray analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High‐Temperature Compression Deformation Behavior of Fine‐Grained Carbon‐Bonded Alumina

Carbon‐bonded alumina with 33 wt% residual carbon was tested in compression at room temperature and at temperatures between 700°C and 1500°C in quasi‐static tests, creep tests, and stress relaxation tests. Therefore, a new high‐temperature test set up with inert gas chamber and inductive heating was used. The tests were accomplished by investigations of microstructure and Young's modulus. At room temperature, the results exhibit a pronounced hysteresis for the first loading cycle, which almost completely disappeared in subsequent cycles. The creep tests showed characteristic curves for compression whereas primary and secondary (stationary) creep occurred. Above 1000°C, a strong increase in creep rate was detected, whereas almost no creep was observed below this temperature. All creep curves were approximated with the models of logarithmic and Andrade creep. The activation energy for creep was found to be 263 kJ/mol above 1150°C. The resistance against stress relaxation showed an anomaly with a minimum between 1000°C to 1200°C and a maximum between 1300°C and 1400°C.     

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%.     

Effect of Thermal Exposures on the Strengths of Nextel™ 550 and 720 Filaments

The effects of thermal exposure on the strengths of Nextel™ 550 and 720 tows, bare and coated with carbon, were determined by room-temperature tensile testing of single filaments extracted from tows that had been exposed to different thermal environments (i.e., air or vacuum) at temperatures from 550° to 1400°C. The results help define the allowable composite processing conditions when using these tows. A 28% drop in the strength of Nextel 550 filaments occurred after a thermal exposure at 1100°C for 2 h in air. After an exposure of 1300°C/2 h/air, a strength degradation of ∼47% resulted. Filaments exposed above 1100°C under vacuum showed more severe strength degradation than filaments exposed in air. The observed strength degradation may stem from a combination of phase transformations of the alumina, the onset of mullite crystallization, and/or exaggerated mullite grain growth. Strength after heat treatment under vacuum at 1050° and 1150°C did not deteriorate as rapidly as after heat treatment under vacuum between 950° and 1050°C or between 1150° and 1250°C. This may be a result of the competition between healing of flaws by the amorphous silica and its evaporation (leading to an increase in its viscosity or loss) and/or densification of the filaments. Nextel 720 filaments exhibited about 9% strength loss after an exposure at 1100°C/2 h/air. The filaments maintained 75% of their strength after a 1300°C/2 h/air heat treatment. The observed strength degradation may stem from thermal grooving, grain growth, and/or annealing of the mullite subgrain boundaries. Thermal exposure of >10 h at 1300°C was required to produce measurable grain growth. Strength loss between 1200° and 1300°C (air heat treatment) was not as great as between 1100° and 1200°C or 1300° and 1400°C.     

Creep behaviour of alumina/YAG nanocomposites obtained by a colloidal processing route

The high temperature creep behaviour (1200–1400 °C and 30–250 MPa) of high-purity alumina (A) and an alumina/YAG nanocomposite (AY) prepared by using a colloidal processing route has been studied. Creep parameters were correlated with microstructural features in order to determine the dominant creep mechanisms in both materials.It was found that the creep rate value of AY was 1 order of magnitude lower than the one of undoped alumina A. The creep mechanism for AY was found to be lattice diffusion (Nabarro–Herring) compared to a combination of grain boundary (Coble) and lattice diffusion for A. When the slow crack growth region of both materials was compared, a significant improvement was observed, i.e. the slow crack growth region of alumina shifted to nearly 2.5 times the stresses applied for AY at the temperatures of 1200, 1300 and 1400 °C.     

Effect of thermal exposure on the microstructure and strength of an alumina-silica ceramic fiber

The microstructure and mechanical properties of an alumina-silica ceramic fiber after thermal exposure at 1100–1300°C were investigated by X-ray diffraction, nuclear magnetic resonance, scanning electron microscopy, transmission electron microscopy analyses and room temperature tensile strength test. The results showed that the fiber was composed of γ-A1₂O₃ and amorphous SiO₂. A phase reaction of γ-A1₂O₃ and amorphous SiO₂ occurred when thermal exposure temperature exceeded 1150°C, and a new mullite phase formed. The grain size of the newly formed mullite increased with the increase of exposure temperature. Both the phase transition and grain growth of mullite had a significant impact on the mechanical properties of the fiber. Tensile strength of the fiber decreased slightly when thermal exposure temperature was below 1150°C, while the strength retention of the fiber decreased sharply to 65.36% as exposure temperature rose to 1200°C. A higher dispersion of tensile strength was also observed at higher exposure temperatures, as revealed by the Weibull statistical model.     

Electrospun mullite nanofibers derived from diphasic mullite sol

Fine‐grained mullite nanofibers derived from the diphasic mullite sol were successfully fabricated by electrospinning and subsequent pyrolysis at 1500°C. Polymethylsiloxane and aluminum tri‐sec‐butoxide were selected as the silicon and aluminum source to synthesize the diphasic sol. Results show that the weight loss of mullite precursor fibers in our work was about 60 wt.%, which is similar with that of fibers fabricated using the monophasic sol. This low weight loss was mainly attributed to the high ceramic yield of polymethylsiloxane and low introduced polyvinylpyrrolidone content, which ensures the integrity of fiber morphology during the sintering process. Mullite fibers with 216 nm average diameter were fabricated after sintered at 1500°C and the corresponding grain size was only ~100 nm, much smaller than that in mullite fibers derived from monophasic sols. Therefore, it can be predicated that mullite fibers in this work should possess a higher mechanical strength than those derived from monophasic sols when the sintering temperature was higher than 1400°C and therefore was an ideal starting materials for the fabrication of mullite nanofibrous ceramics used as the high‐temperature thermal insulation materials.     

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.     

Mullite–Nickel Magnetic Nanocomposite Fibers Obtained from Electrospinning Followed by Thermal Reduction

Mullite–nickel nanocomposite fibers with Ni nanoparticles of controllable size, dispersion, and consequent magnetic properties were fabricated using sol–gel/electrospinning method, followed by thermal reduction. The fibers were electrospun from an aqueous solution containing sol–gel mullite precursor and nickel nitrate. These fibers were then heat treated in the reducing atmosphere between 550°C and 750°C to achieve fine‐dis persed metallic Ni nanoparticles (NPs). After the Ni²⁺ was reduced to Ni NPs at 750°C for 10 h, the fibers were then directly transformed to the mullite fibers at 1000°C without the undesirable intermediate spinel phase. In many high‐temperature applications, mullite is the desired phase than spinel. If not fully reduced, the Ni²⁺ cations induce early precipitation of spinel phase before mullite can be formed. This spinel phase was a solid solution between Al₂NiO₄ and Al‐Si spinels, which later reacted with the residual silica and formed a mixture of mullite and spinel at 1400°C. The formation of spinel phase was suppressed or fully eliminated with chemically reducing Ni²⁺ to metal NPs. The average size of nickel NPs within the fibers was ~20 nm, insensitive of the Ni concentration and reducing temperature. However, the Ni NPs on the fiber surface grew as large as ~80 nm due to fast surface diffusion. The magnetic nanocomposites exhibited ferromagnetism with saturation magnetization (M_s) close to pure nickel of the same nominal weight, but coercivity (H_c) much smaller than the bulk nickel, indicating the nature of bimodal magnetic nanoparticle distributions. The majority of small Ni NPs (~20 nm) within the fibers exhibited superparamagnetism, while the minor portion of relatively large NPs (50–80 nm) showed ferromagnetism.     

Tensile creep properties and damage mechanisms of 2D-SiCf/SiC composites reinforced with low-oxygen high-carbon type SiC fiber

Tensile creep properties of 2D-SiC_f/SiC composites reinforced with low-oxygen high-carbon type SiC fibers were studied in vacuum at 1300°C∼1430°C. The fracture morphology was observed by scanning electron microscopy and the damage of fiber in 2D-SiC_f/SiC composites was characterized by nanoindentation. Moreover, the microstructure of the composite was investigated by high-resolution transmission electron microscopy. The results show that rupture time is much shortened and steady-state creep rate increase three orders of magnitude when creep temperature is higher than 1400°C. There are two different creep damage mechanisms due to the decrease of interfacial bonding strength at high temperature. The amorphous SiO_xC_y phase in the fibers can crystallize into SiC and C and the SiC grain grows in the fiber. The microstructural changes lead to the decrease of fiber strength and degrade the creep properties of the composite above 1400°C.     

Facile one-step precursor-to-aerogel synthesis of silica-doped alumina aerogels with high specific surface area at elevated temperatures

Silica-doped alumina aerogels offer the potential alternative to the applications as thermal insulators, catalysis, or catalytic support at elevated temperatures. However, the production process of silica-doped alumina aerogels was complicated and time-consuming. We developed a one-step precursor-to-aerogel method of silica-doped alumina aerogels with high specific surface area and thermal stability. Compared to conventional methods, the developed method reduced time and solvent waste of alumina-based aerogels production. Here, we investigated the alumina aerogels doped with silica to stabilize γ-phase at higher temperatures. XRD, FTIR, TEM, TG-DSC, and BET analysis results showed that silica stabilized the γ-Al₂O₃ at 1200 °C. The stabilization mechanism analysis showed that silica addition could significantly hinder the contact among alumina particles and the formation of necks in the sintering process, thereby retarding the transition of γ–θ phase and maintaining the high specific surface area at elevated temperatures. Silica and alumina particles formed mullite at 1200 °C, which could suppress α-phase transformation. In addition, silica-doped alumina aerogels exhibited the high specific surface area of 311 m²/g at 1000 °C and 146 m²/g at 1200 °C when the silica content was in the range of 10.6–13.1 wt%.     

Kinetics and mechanisms for the densification and grain growth of the α-alumina fibers isothermally sintered at elevated temperatures

Understanding the densification and grain growth processes is essential for preparing dense alumina fibers with nanograins. In this study, the alumina fibers were prepared via isothermal sintering at 1200, 1300, 1400, and 1500 °C for 1–30 min. The phase, microstructure, and density of the sintered fibers were investigated using XRD, SEM, and Archimedes methods. It was found that the phase transformation during the isothermal sintering enhances the densification of Al₂O₃ fibers in the initial stage, while the pores generated during the phase transformation retard the densification in the later period. The kinetics and mechanisms for the densification and grain growth of the fibers were discussed based on the sintering and grain growth models. It was revealed that the densification process of the fibers sintered at 1500 °C is dominated by the lattice diffusion mechanism, while the samples sintered at 1200–1400 °C are dominated by the grain boundary diffusion mechanism. The grain growth of the Al₂O₃ fibers sintered at 1200–1300 °C is governed by surface-diffusion-controlled pore drag, and that sintered at 1400 °C is dominated by lattice-diffusion-controlled pore drag.     

Foreign element doping and thermal stability of alumina aerogels

The addition of foreign elements is considered as an effective method to improve the thermal stability of alumina aerogels at a higher temperature. However, the location and stabilizing mechanism of the foreign elements in the alumina aerogel have not been carefully studied. In this work, Si or La was introduced into the network of alumina aerogels through a sol-gel strategy. The Si-doped alumina aerogel maintained high surface area (92 m²/g) and pore volume (0.572 cm³/g) even at 1300°C. The dopants prevented α-Al₂O₃ transformation at elevated temperatures (1200°C–1300°C). The distribution of foreign ions and their stabilizing mechanism were discussed in detail. The doped alumina aerogels reinforced by mullite fiber felt, with quite low density and thermal conductivity, can be used as high-temperature thermal insulations.