Increasing the tensile strength of oxide ceramic matrix mini-composites by two-step sintering

Adapting conventional sintering (CS) techniques of monolithic ceramics for the production of oxide ceramic matrix composites (Ox-CMCs) comes along with a few drawbacks, such as fiber degradation. Thus, the applicability of two-step sintering (TSS) for the production of Ox-CMCs based on Nextel™ 610 fibers and porous alumina matrix is investigated in this study for the first time. Uniaxial tensile tests were performed to evaluate the performance of mini-composites produced by TSS and compared with those produced by CS. Parameters known for influencing the mechanical behavior of the mini-composites, such as grain size, porosity, shrinkage, as well as matrix properties, were analyzed. Both sintering techniques resulted in similar grain size distributions, whereas TSS showed higher total porosity and lower amount of sintering-induced cracks. As a result, TSS samples showed a higher tensile strength of 230±27 MPa when compared to 133±8 MPa for CS. In general, it was observed that most of the densification happens during the first phase of TSS, while the matrix is slowly strengthened during the second step. Therefore, the reported TSS process is a very promising and easy-to-apply heat treatment for producing Ox-CMCs with controlled microstructure.     

Electromagnetic characteristics and microstructure stability of Nextel 610 fiber after heat treatment

The thermal and microstructure stability of Nextel 610 fibers has great influence on high-temperature application of Nextel 610 fiber-reinforced ceramic matrix composites. In this work, Nextel 610 fibers were heat treated at 500–700 °C in vacuum and 800–1100 °C in Ar atmosphere, respectively. The sizing agent on Nextel 610 fiber surface could be decomposed into pyrolytic carbon, SiC and gaseous little molecules at lower temperatures, otherwise it was decomposed mainly in the form of gaseous little molecules at higher temperatures, so that the complex permittivity firstly increased and then decreased with the increasing of temperatures. The results showed that the annealed Nextel 610 fiber (T>900 °C) could be regarded as electromagnetic wave transparent fibers, while the tensile strength had declined by half when the temperature increased to 1100 °C. Therefore, Nextel 610 fibers after being annealed at higher temperatures could be further used as reinforcement to prepare high temperature ceramic matrix composites for electromagnetic wave absorption and transparent applications.     

Zirconia-alumina multiphase ceramic fibers with exceptional thermal stability by melt-spinning from solid ceramic precursor

Zirconia-alumina multiphase ceramic fibers with 80 wt% (Z80A20 fiber) and 10 wt% (Z10A90 fiber) proportions of zirconia were prepared via melt-spinning and calcination from solid ceramic precursors synthesized by controllable hydrolysis of metallorganics. The zirconia-alumina multiphase fibers had a diameter of about 10 µm and were evenly distributed with alumina and zirconia grains. The Z80A20 and Z10A90 ceramic fibers had the highest filament tensile strength of 1.78 GPa and 1.87 GPa, respectively, with a peak value of 2.62 GPa and 2.71 GPa. The Z80A20 ceramic fiber has superior thermal stability compared to the Z10A90 ceramic fiber and a higher rate of filament strength retention due to the stability in grain size. After heat treatment at 1100 °C, 1200 °C, and 1300 °C for 1 h respectively, the filament tensile strength retention rate of Z80A20 ceramic fibers was 87 %, 80 %, and 40 %. While Z10A90 ceramic fiber was fragile after being heated at 1300 °C. The results showed that the high zirconia content facilitated the fiber's thermal stability.     

Preparation and mechanical properties of the 2.5D ASf/ZrO2 composites after high-temperature heat treatment

In the paper, the aluminosilicate fiber-reinforced zirconia (AS_f/ZrO₂) ceramic composites were successfully fabricated by polymer impregnation and pyrolysis (PIP) method. The microstructure and high-temperature mechanical properties of the original composites were well studied. The results revealed that the composites could maintain the stability of microstructure at 1000 °C. The flexural strength increased from 58.82 ± 2.83 MPa to 88.74 ± 6.20 MPa and the flexural modulus increased from 29.26 ± 4.67 GPa to 40.76 ± 8.76 GPa. The thermal exposure improved the interfacial bonding and made the load transfer more effective. After heat treatment from 1200 °C to 1400 °C, the flexural strength gradually declined due to the crystallization of the AS fibers and ZrO₂ matrix, while the flexural modulus increased in a completely different trend. After heat treatment at 1400 °C, the composites could maintain a flexural strength of 66.95 ± 4.24 MPa with a flexural modulus of 60.42 ± 7.25 GPa. But the fracture mode gradually evolved to brittleness.     

Thermal exposure effects on the long‐term behavior of a mullite fiber at high temperature

The behavior of an oxide fiber at elevated temperatures was analyzed before and after thermal exposures. The material studied was a mullite fiber developed for high‐temperature applications, CeraFib 75. Heat treatments were performed at temperatures ranging from 1200°C to 1400°C for 25 hours. Quantitative high‐temperature X‐ray analysis and creep tests at 1200°C were carried out to analyze the effect of previous heat treatment on the thermal stability of the fibers. The as‐received fibers presented a metastable microstructure of mullite grains with traces of alumina. Starting at 1200°C, grain growth and phase transformations occurred, including the initial formation of mullite, followed by the dissociation of the previous alumina‐rich mullite phase. The observed transformations are continuous and occur until the mullite phase reaches a state near the stoichiometric 3/2 mullite. Only the fibers previously heat treated at 1400°C did not show further changes when exposed again to 1200°C. Overall, the heat treatments increased the fiber stability and creep resistance but reduced the tensile strength. Changes observed in the creep strain vs. time curves of the fibers were related to the observed microstructural transformations. Based on these results, the chemical composition of the stable mullite fiber is suggested.     

Scheelite coatings on SiC fiber: Effect of coating temperature and atmosphere

Scheelite coating was deposited on SiC fiber tows from various liquid-phase precursors followed by heat treatments between 900 °C and 1100 °C in different atmospheres. The tensile strength was fully retained for the coated fibers treated at 900 °C in vacuum. Subsequent heat treatment at 1100 °C in Ar had little effect on the fiber strength, which is explained by the excepted good thermal stability between the scheelite coating and SiC fiber. However, larger strength degradation and poor spool ability of coated fibers prepared in Ar/air were found. Assisted oxidation of SiC fiber by calcium salts is suggested to be responsible for the much larger strength degradation of fibers prepared in Ar/air.     

Normal and Abnormal Grain Growths in BaTiO3 Fibers

The grain growth mechanisms along the BaTiO₃ fibers were studied between 1150°C and 1250°C. The normal grain growth always reached a stagnant stage after certain heat‐treatment duration caused by the surface pinning effect. However, the abnormal grain growth (AGG) was not pinned by such surface effect, and can grow continuously. The confined normal grain (or matrix grain) size provides the driving force for AGG. The fiber diameter has an important influence on the grain growth behaviors. Submicrometer fibers have relative small stagnant grain sizes, resulting in large driving force for AGG. Abnormal grain growth occurred below 1200°C in the submicrometer diameter fibers, but was not observed at the same temperature in the fibers with diameter of above 1 μm. Due to the large AGG driving force, large number densities of abnormal grains were observed in submicrometer fibers, resulting in “bamboo‐like” microstructure. Fibers with diameters of 1–2 μm were able to be converted into single crystal fibers up to several tens of micrometers due to the relative small AGG driving forces.     

Heat treatment effects on microstructure and properties of CVI SiC/SiC composites with Sylramic™-iBN SiC fibers

Chemical-vapor-infiltrated (CVI) SiC/SiC composites with Sylramic?-iBN SiC fibers and CVI carbon, BN, and a combination of BN/C interface coating were heat treated in 0.1-MPa argon or 6.9-MPa N₂ at temperatures to 1800 °C for exposure times up to 100 hr. The effects of thermal treatment on constituent microstructures, in-plane tensile properties, in-plane and through-the-thickness thermal conductivities, and creep behavior of the composites were investigated. Results indicate that heat treatment affected stoichiometry of the CVI SiC matrix and interface coating microstructure, depending on the interface coating composition and heat treatment conditions. Heat treatment of the composites with CVI BN interface in argon caused some degradation of in-plane properties due to the decrease in interface shear strength, but it improved creep resistance significantly. In-plane tensile property loss in the composites can be avoided by modifying the interface composition and heat treatment conditions.     

Polyethylene fibers-polyethylene matrix composites: Preparation and physical properties

Drawing on the difference in melting points of UHMPE fiber (150°C) and HDPE matrix (130°C), single-polymer composites were fabricated under various processing conditions. Because of the chemical similarity of the composite components, good bonding at the fiber-matrix interface could be expected. The matrix, the fiber, and unidirectional composite laminae were studied using TMA and DSC analyses, a hot-stage crystallization unit attached to a polarizing microscope, and an universal tensile testing machine. The TMA showed negative thermal expansion of the fiber over the complete temperature range of the experiment. Three regimes of contraction according to the values of the thermal expansion coefficient were detected. DSC analyses of either the fiber or the composite specimens did not show any appreciable changes after various thermal treatments. They also showed no evidence of fiber relaxation during manufacture, probably because of the pressure-related transverse constraint. The tensile strength and modulus values of the composite appeared to be fairly high and close to those reported for other composites reinforced with polyethylene (PE) fibers. An apparent maximum on the temperature dependencies of tensile properties was observed. A study of the matrix microstructure did not give any proof of transcrystalline growth at the fiber-matrix interface even for chemical or plasma surface-treated fibers. © 1993 John Wiley & Sons, Inc.     

Mechanical properties of ceramic matrix composites with siloxane matrix and liquid phase coated carbon fiber reinforcement

In order to evaluate the benefits of continuous liquid phase coating (CLPC) for carbon fibers, coated fibers as well as uncoated fibers were applied in the preparation of unidirectionally reinforced ceramic matrix composites (CMCs) with polysiloxane based matrix. Fibers coated with precursor based ceramic or carbon coatings were transferred into prepregs by continuous fiber impregnation with liquid polysiloxane and filament winding. The wet prepregs were cut to shape, laminated and then pressed and cured in the mold at 150 °C for 1 h. The cured polymeric matrix composites were calcined and densified by subsequent precursor infiltration/calcination cycles. The flexural strength of the CMCs was measured by 4-point bending tests, the microstructure was determined by optical and scanning electron microscopy. The application of CLPC coated fibers led to a significant improvement in composite strength and young's modulus compared to identical reference samples with uncoated carbon fibers.     

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.     

Alumina fiber-reinforced silica matrix composites with improved mechanical properties prepared by a novel DCC-HVCI method

A novel direct coagulation casting via controlled release of high valence counter ions (DCC-HVCI) method was applied to prepare the alumina fiber-reinforced silica matrix composites with improved mechanical properties. In this method, the silica suspension could be rapidly coagulated via controlled release of calcium ions from calcium iodate and pH shift by hydrolysis of glycerol diacetate (GDA) at an elevated temperature. The influence of tetramethylammonium hydroxide (TMAOH) dispersant amount, volume fraction and calcium iodate concentration on the rheological properties of suspensions was investigated. Additionally, the effect of alumina fiber contents on the mechanical properties of alumina fiber-reinforced silica matrix composites was studied systematically. It was found that the stable suspension of 50 vol% solid loading could be prepared by adding 2.5 wt% TMAOH at room temperature. The addition of 0–15 wt% alumina fibers had no obvious effect on the viscosity of the silica suspension. The controlled coagulation of the suspension could be achieved by adding 6.5 g L⁻¹ calcium iodate and 1.0 wt% GDA after treating at 70 °C for 30 min. Compressive strength of green bodies with homogeneous microstructure was in the range of 2.1–3.1 MPa. Due to the fiber pull-out and fracture behaviors, the mechanical properties of alumina fiber-reinforced composites improved remarkably. The flexural strength of the composite with 10 wt% alumina fibers sintered at 1350 °C was about 7 times of that without fibers. The results indicate that this approach could provide a promising route to prepare complex-shaped fiber-reinforced ceramic matrix composites with uniform microstructure and high mechanical properties.     

Influence of graphitization treatment on microstructure and flexural strength of C/C-ZrC-SiC composites fabricated via reactive melt infiltration

C/C-ZrC-SiC composites were prepared by chemical vapor infiltration (CVI) and molten salt assisted reactive melt infiltration (RMI). The microstructure of low density and high density C/C composites without graphitization (LC/HC) and graphitization at 2000 °C (LCG/HCG) were compared. Moreover, the effects of graphitization of LC and HC on the microstructure and flexural strength of C/C-ZrC-SiC composites were investigated in detail. The composites prepared by infiltration of LC and LCG had lower flexural strength, 220.01 ± 21.18 MPa and 197.94 ± 19.05 MPa, respectively. However, the composites prepared by HC and HCG presented higher flexural strength, 308.76 ± 12.35 MPa and 289.62 ± 8.70 MPa, respectively. This was due to the phenomenon of fiber erosion in both LC and LCG during the RMI process. After graphitization, the flexural strength of C/C-ZrC-SiC composites prepared by RMI decreased, but the fracture behavior of the composites tends to be more mild. The decreased strength of the composites were caused by the increased matrix cracks, fiber damage in high temperature and the weak interfacial bonding. The improve of failure behavior of the composites was due to interface debonding between the fiber and matrix, and composites can consume the fracture energy through fiber pull-out.     

Synthesis and microstructure evolution of β-Sialon fibers/barium aluminosilicate (BAS) glass-ceramic matrix composite with enhanced mechanical properties

Dense Sialon fibers/barium aluminosilicate (BAS) matrix self-reinforced composite was synthesized by one-step method without applying pressure before or during sintering process. In this work, BAS matrix and internal Sialon fibers were synthesized successfully by directly sintering precursor powders at 1400°C for 4 h. The BAS is not only introduced as a structural matrix material, but also as an effective liquid phase sintering aid to attain full densification bulk sample. The results show that the diameter of fibers is about 100–200 nm, and the quantity of the fibers can be changed with different temperatures. The obtained Sialon fibers/BAS matrix composites exhibit better toughness due to fiber bridging, crack deflection, and pullout. The sample with 3.5 wt% carbon content has maximum value of flexural strength (74.5 ± 3.5 MPa) and fracture toughness (3.2 ± 0.20 MPa·m^1/2). The growth of the Sialon fibers follows a vapor-liquid-solid (V-L-S) mechanism. These findings featured with a green and simple preparation process provide a facile strategy to design and fabricate the bulk ceramic matrix composites in complex shapes and different sizes.     

Continuous aluminum oxide-mullite-hafnium oxide composite ceramic fibers with high strength and thermal stability by melt-spinning from polymer precursor

Continuous aluminum oxide-mullite-hafnium oxide (AMH) composite ceramic fibers were obtained by melt-spinning and calcination from polymer precursor that synthesized by hydrolysis of the aluminum isopropoxide, dimethoxydimethylsilane and hafnium alkoxide. Due to the fine diameter of 8–9 µm, small grain size of less than 50 nm and the composite crystal texture, the highest tensile strength of AMH ceramic fibers was 2.01 GPa. And the AMH ceramic fibers presented good thermal stability. The tensile strength retention was 75.48% and 71.49% after heat treatment at 1100 °C and 1200 °C for 0.5 h respectively, and was 61.57% after heat treatment at 1100 °C for 5 h. And the grain size of AMH ceramic fibers after heat treatment was much smaller than that of commercial alumina fibers even when the heat treatment temperature was elevated to 1500 °C, benefited by the grain size inhibition of monoclinic-HfO₂ (m-HfO₂) grains distributed on the boundary of alumina and mullite grains.     

Preparation and characterization of Nextel 720/alumina ceramic matrix composites via an improved prepreg process

In this work, the Nextel 720 continuous fiber reinforced alumina ceramic matrix composites (CMCs) were prepared by an improved prepreg process. The alumina matrix was derived from aqueous slurry, which consisted of organic glue, alumina sol, nanometer alumina powders, and micrometer alumina powders. This design provided a densely packed matrix for the CMC, and made the whole process relatively simple. The ratio of different alumina components in aqueous slurry was optimized to obtain good sintering activity, high thermal resistance, and excellent mechanical properties simultaneously. Furthermore, a preceramic polymer of mullite was used to strengthen the ceramic matrix through a multiple infiltration process. The final CMC sample achieved a high flexural strength of 255 MPa and a good high-temperature stability. After 24 h of heat treatment at 1100°C, 85% of the maximum flexural strength still had been retained.     

Monazite Coatings on Fibers: I, Effect of Temperature and Alumina Doping on Coated-Fiber Tensile Strength

Monazite was continuously coated onto Nextel 720 fibers, using an aqueous precursor and in-line heat treatment at 900°–1300°C. Some experiments were repeated with alumina-doped precursors. Coated fibers were heat-treated for 100 h at 1200°C. Coatings were characterized by optical microscopy, scanning electron microscopy, and analytical transmission electron microscopy. Coated-fiber tensile strengths were measured by single-filament tensile tests. The precursors were characterized by X-ray diffractometry, differential thermal analysis/thermogravimetric analysis, and mass spectrometry. Coated-fiber tensile strength was lower for fibers coated at higher deposition temperatures. Heat treatment for 100 h at 1200°C decreased tensile strength further. The coatings were slightly phosphate-rich and enhanced alumina grain growth at the fiber surface, but phosphorus was not detected along the alumina grain boundaries. Fibers with alumina-doped coatings had higher tensile strengths than those with undoped coatings after heat treatment for 100 h at 1200°C. Alumina added as α-alumina particles gave higher strengths than alumina added as colloidal boehmite. Alumina doping slowed monazite grain growth and formed rough fiber–coating interfaces after 100 h of heat treatment at 1200°C. Possible relationships among precursor characteristics, coating and fiber microstructure development, and strength-degradation mechanisms are discussed in this paper.     

Preparation and crystallization of forsterite fibrous gels

Transparent forsterite fibrous gels were prepared from the hydrolysis of alkoxide precursor sols with acetic acid and water, and the crystallization process of gel fibers was studied after heat treatments up to 1500 °C. Appropriate amount of acetic acid not only promoted the formation of spinnable linear-type polymeric species, but also enhanced the chemical homogeneity and reduced the crystallization temperature of the resultant gels. On heating, fibrous gels started to crystallize into forsterite at 550 °C as investigated by infrared spectrum, X-ray diffraction and thermal analysis. Single phase forsterite fiber thus could be obtained up to 1500 °C when the amount of hydrolysis water was limited. However, fibrous gel derived from the high-water-content sol displayed a few secondary phases of the magnesia (MgO) and protoenstatite (MgSiO₃) following heating at 1000 and 1400 °C, respectively; similarly, xerogels derived from without or with insufficient amount of acetic acid also revealed the segregation of second phases on heating. The synthesized forsterite fibers displayed nanocrystalline structure up to 1100 °C. On heating to 1300 °C, fired fibers exhibited grain growth into around 0.3–0.5 μm in size, with the room temperature dielectric constants of around 6.8–7.2 (at 1 MHz).     

High-temperature properties and interface evolution of silicon nitride fiber reinforced silica matrix wave-transparent composite materials

In order to improve the high-temperature performance of wave-transparent materials especially for the high-speed aircrafts application, filament winding combined with sol-gel method was adopted to the fabrication of unidirectional silicon nitride fiber reinforced silica matrix composites. The mechanical properties and the interface evolution at high temperatures were investigated. The results show that the composite sintered in N₂ maintains a flexural strength of 210MPa at up to 1200°C, while its counterpart prepared in air experiences a dramatic reduction to about 73MPa. The degradation is due to the partial oxidation of silicon nitride fibers at the fiber matrix interface. Besides, it is also notable that the bending strength of these two composites undergoes a similar growth from about 160 to 210MPa when tested under 900°C, which can be explained by the release of thermal stress on the silicon nitride fibers.     

Preparation of carbon fiber/Mg-doped nano-hydroxyapatite composites under low temperature by pressureless sintering

In order to protect carbon fibers (CF) from oxidation damage during sintering process, rod-like Mg-doped nano-hydroxyapatite (Mg-nHA) with an increased thermal decomposition temperature and reduced sintering temperature was synthesized by hydrothermal method. The synthesized bone-like Mg-nHA with similar composition and morphology to bone apatite was used as the matrix to prepare CF reinforced Mg-nHA composites (CF/Mg-nHA) at a low temperature of 700 °C by pressureless sintering. The increase of temperature slightly influenced the growth of Mg-nHA prepared by hydrothermal method from 160 °C to 200 °C. The Mg-nHA were short and rod-like in structure with a length of approximate 100 nm. When doping 1% magnesium, the decomposition temperature of Mg-nHA increased by 100 °C compared with that of nHA. This can protect CF from oxidation damage which is often encountered when sintering CF reinforced hydroxyapatite composites at high temperature and enhance reinforcing effects of CF. The bending strength of CF/Mg-nHA with 1 wt% CF was 8.51 MPa, which increased by 19.5% compared with Mg-nHA. Alternatively, the rod-like Mg-nHA was prepared on the surface of CF by electrochemical deposition and Mg-nHA coated CF was used to reinforce Mg-nHA, the coefficient of thermal expansion mismatch between CF and HA matrix could be mitigated. The compressive strength of Mg-nHA coated CF reinforced Mg-nHA (CF/Mg-nHA/Mg-nHA) composites with 0.5% CF sintered at 800 °C were 41.3 ± 1.56 MPa, which was attributed to the improved strengthening effect of CF and the good interface between CF and Mg-nHA matrix.