High density carbon fiber/boron nitride matrix composites: Fabrication of composites with exceptional wear resistance

This paper describes the fabrication of high density (ρ ∼ 1.75 g/cc) composites containing a hybrid (carbon and boron nitride), or complete boron nitride matrix. The composites were reinforced with either chopped or 3D needled carbon fibers. The boron nitride was introduced via liquid infiltration of a borazine oligomer that can exhibit liquid crystallinity. The processing scheme was developed for the chopped carbon fiber/boron nitride matrix composites (C/BN) and later applied to the 3D carbon fiber reinforced/boron nitride matrix composites (3D C/BN). The hybrid matrix composites were produced by infiltrating the borazine oligomer into a low density 3D needled C/C composite to yield 3D C/C-BN. In addition to achieving high densities, the processing scheme yielded d₀₀₂ spacings of 3.35 Å, which afforded boron nitride with excellent hydrolytic stability. The friction and wear properties of the composites were explored over the entire energy spectrum for aircraft braking using an inertial brake dynamometer. The C/BN composites outperformed both the previously reported C/C-BN and chopped fiber reinforced C/C. The high density 3D C/BN performed as well as both the 3D C/C and the C/BN. The 3D C/C-BN provided outstanding wear resistance, incurring nearly zero wear across the entire testing spectrum. The coefficient of friction was relatively stable with respect to energy level, varying from 0.2 to 0.3.     

Microstructures and tribological properties of carbon/carbon-boron nitride composites fabricated by powdered additives and chemical vapor infiltration

The carbon fiber reinforced/carbon-boron nitride (C/C-BN) dual matrix composites were fabricated via adding hexagonal boron nitride (h-BN) powders into the needled carbon felt and subsequent chemical vapor infiltration (CVI) process. An experimental investigation was performed to study the influences of BN volume content on the microstructures and tribological properties of C/C-BN composites. The results indicate that the pyrolytic carbon (PyC) in the C/C-BN composites is regenerative laminar (ReL) due to the inducement of BN powders during CVI process, whereas the PyC in the C/C composite is classic smooth laminar. Additionally, the friction coefficients of C/C-BN composites with three different BN contents in volume fractions (4.5, 9 and 13.5 vol%) are all higher compared to the reference C/C composite (0.22). Note that the highest coefficient of friction (0.29) is obtained when the BN volume content in the C/C-BN composite is 9 vol%. Moreover, the linear and mass wear rates of C/C-BN composites as well as the 30CrSiMoVA counterparts are significantly decreased with the increase of BN volume content. The favorable friction and wear properties of C/C-BN composites are attributed to the synergistic effect induced by the ReL PyC and BN. The microstructural variation of C/C composites modified by h-BN could improve the compatibility between the C/C-BN composites and 30CrSiMoVA counterpart, resulting in an enhanced adhesive attraction between the wear debris and the surface of 30CrSiMoVA counterpart. Furthermore, the investigations concerning the friction surfaces indicate that the formation of sheet-like friction films with large areas are more easily to occur on the surfaces of 30CrSiMoVA counterparts mating with the C/C-BN composites rather than mating with the C/C composite.     

Effect of heat treatment on the tribological behavior of 2D carbon/carbon composites

The effect of high temperature heat treatment on the tribological behavior of carbon/carbon (C/C) composites has been investigated. C/C composite preforms were made from 1K PAN plain carbon cloth, and densified using rapid directional diffusion (RDD) CVI processes. Four specimens treated at 1800, 1800+2000, 2000, and 2300 °C, respectively, were prepared. A ring-on-ring specimen configuration was used to simulate aircraft brakes. The brake initial angular velocity ranged from 1800 to 7500 rpm (6.2-26.0 m s⁻¹ average linear sliding velocity). The specific pressure and moment of inertia were 392-784 kPa and 0.25-0.31 kg m², respectively (1.9-42.3 MJ m⁻² kinetic energy loading per unit friction surface area). The results showed that the stability of the brake moment-time curves increased with increasing heat treatment temperature (HTT) for the four composites, and those treated at 2300 °C possessed the lowest initial brake moment peak ratio values (from 1.1 to 1.3). The high degree of graphitization and low shear forces of the matrix carbon resulting from the high HTT could allow friction films to develop and reduce those values under the present brake conditions. The friction coefficients of four RDD CVI C/C composites decreased with an increase in specific pressure. The resulting changes in the friction coefficient of the four composites due to the specific pressure changes have basically nothing to do with the interface temperature under those conditions. According to the practical brake conditions, the friction properties of RDD CVD C/C composites could be improved by regulating the structure of the brake discs, changing the specific pressure exerted on the discs and the heat treatment. The linear wear rates of the four materials increased with increasing HTT. The composites treated at 2000 °C had both high enough friction coefficients and the lower linear wear rates. The different heat treatment methods at 2000 °C had no obvious effect on the friction and wear properties of RDD CVI C/C composites.     

Braking Behavior of C/SiC Composites Prepared by Chemical Vapor Infiltration

Carbon fiber-reinforced silicon carbide matrix composites have the potential to overcome the shortcoming of the currently used carbon/carbon friction materials in aircraft brakes. In this article, the carbon/silicon carbide (C/SiC) composites were prepared by chemical vapor infiltration method, and the brake disks with different densities and component content were finally obtained. The friction coefficient and friction stability can be significantly improved by increasing both material density and carbon content. When the density of C/SiC composite is 2.3 g/cm³, the coefficient of friction measured is 0.23, the coefficient of friction stability remains about 0.43, the liner wear rate is less than 9.3 μm/cycle, and the weight wear rate is less than 9.1 μm/cycle. The rapid increase of friction coefficient approaching the end of braking is mainly related to the increasing of surface temperature in a short time and the enhanced adhesion and abrasion of contact conjunctions and asperities. The C/SiC composites exhibited a good stability of braking against fading versus the braking number and surface temperature. The surfaces of C/SiC brake disks were covered with wear debris including the fragment of carbon fibers after the braking tests. The wear on the surfaces is significantly determined by cyclic mechanical and thermal stresses, which result in the micro-cracks in the SiC matrix, the thin flakes of the surface materials as well as the grooves.     

Friction behaviors of carbon/carbon composites with different pyrolytic carbon textures

Friction and wear properties of carbon/carbon (C/C) composites with a smooth laminar (SL), a medium textured rough laminar (RL) and a high textured RL pyrolytic carbon texture were investigated with a home-made laboratory scale dynamometer to simulate airplane normal landing (NL), over landing (OL) and rejected take-off (RTO) conditions. The morphology of worn surfaces at different braking levels was observed with scanning electron microscopy. The results show that C/C composites with RL have nearly constant friction coefficients, stable friction curves and proper wear loss at different braking levels, while friction coefficients of C/C composites with SL pyrolytic carbon decrease intensely and their oxidation losses increase greatly under OL and RTO conditions. Therefore, C/C composites with a high and medium textured RL pyrolytic carbon may satisfy the requirements of aircraft brakes. The good friction and wear properties of C/C composites with RL are due to the properties of RL, which leads to a uniform friction film forming on the friction surface.     

Effect of preparation method on the mechanism for oxidation of C/C-BN composites

C/C-BN composites and C_f/BN/PyC composites exhibiting different structures for pyrolytic carbon (PyC) and boron nitride (BN) were studied comparatively to determine their oxidation behavior. This study used five types of samples. Porous C/C composites were modified with silane coupling agents (APS) and then fully impregnated in water-based slurry of hexagonal boron nitride (h-BN); the resulting C/C-BN preforms were densified by depositing PyC by chemical vapor infiltration (CVI), resulting in three types of C/C-BN composites. The other two C_f/BN/PyC composites were obtained by depositing a BN interphase and PyC in carbon fiber preforms by CVI; one was treated with heat, and the other was not. This study was focused on determining how the PyC deposition mechanism, morphology and pore structure were affected by the method of BN introduction. In the 600–900 °C temperature range, the C_f/BN/PyC composites and C/C composites underwent oxidation via a mixed diffusion/reaction mode. The C/C-BN composites had a different pore structure due to the formation of nodules comprising h-BN particles; both interfacial debonding and cracking were reduced, resulting in higher resistance to gas diffusion, lower oxidation rate and larger activation energy (Ea) in the temperature range 600–800 °C. In addition, the mechanism for oxidation of C/C-BN composites gradually exhibited diffusion control at 800–900 °C because the formation of h-BN oxidation products healed the defects. The oxidation mechanism was more dependent on pore structure than on BN structure or content.     

Microstructure and tribological behaviors of C/C–BN composites fabricated by chemical vapor infiltration

In this paper carbon fiber reinforced carbon–boron nitride binary matrix composites (C/C–BN) were prepared by chemical vapor infiltration (CVI). The infiltration of BN in the CVI process was controlled by the diffusion of BCl₃, and BN matrix was distributed homogeneously in the porous carbon fiber reinforced carbon matrix composites (C/C) due to the good infiltration ability of BN. The as-received C/C–BN composites were composed of 92 vol% C and 8 vol% BN. Both the friction coefficient and wear rate of C/C composites decreased significantly by the incorporation of BN. After heat-treated at 1600 °C, the interlayer spacing of CVI BN decreased to 3.36 Å, and CVI BN with high crystalline degree displayed the excellent lubricating effect, leading to the decrease of friction coefficient and wear rate. The improvement of the tribological properties also was partially attributed to the improved oxidation resistance and the formation of friction film by the incorporation of BN matrix.     

Anisotropic tribological behavior of LSI based 2.5D needle-punched carbon fiber reinforced Cf/C–SiC composites

C_f/C–SiC composites were fabricated via liquid silicon infiltration with 2.5D needle-punched carbon fiber reinforced C_f/C composites. The effect of surface topography and carbon content of the C_f/C–SiC composites on the tribological properties was researched by the ball-on-disk reciprocating tribometer. The results indicate that different fiber layers and cross-section of the composites have various surface topography and show significant differences in the friction and wear properties. By the wear morphology and model analyses, the reason for the tribological anisotropy of the composites is that the distribution of carbon and SiC phases in the composites are inhomogeneous caused by the difference of the carbon fiber orientation and the relative content in each layer. Moreover, the wear rate of the short-cut fiber web layer was the lowest and there is an obvious linear decrease in coefficient of friction with increase of carbon content. The present work explains why the tribological properties of the composites are inconsistent and provides a way to adjust the friction properties of composite materials by optimizing the friction surface.     

Oxidation behavior of carbon/carbon-boron nitride composites fabricated by additives and chemical vapor infiltration

Carbon/carbon-boron nitride (C/C-BN) composites were manufactured by adding hexagonal boron nitride (h-BN) powders into carbon fiber preform and a subsequent chemical vapor infiltration (CVI) process for deposition of pyrolytic carbon (PyC). Microstructure and oxidation behavior of carbon/carbon composites with 9?vol% h-BN (C/C-BN9) were studied in comparison to carbon/carbon (C/C) composites. Results showed that with the addition of h-BN powders, a regenerative laminar (ReL) PyC with higher texture was achieved. Note that the introduction of h-BN powder make great contributes to graphitization degree of PyC, leading to larger oxidation activation energy. Moreover, under an air atmosphere, h-BN started to oxidize above 800?°C, and generated molten boron oxide (B₂O₃) which prohibited oxygen diffusion by filling in pores, cracks and other defects. As these reasons mentioned above, after oxidation tests under an air atmosphere, mass losses of C/C-BN9 composites were lower than that of C/C composites at all test temperatures (600–900?°C), indicating that the oxidation resistance of C/C-BN9 composites is better than that of C/C composites.     

Tribological application of carbon nanotubes in a metal-based composite coating and composites

Ni-P-carbon nanotube (CNT) composite coating and carbon nanotube/copper matrix composites were prepared by electroless plating and powder metallurgy techniques, respectively. The effects of CNTs on the tribological properties of these composites were evaluated. The results demonstrated that the Ni-P-CNT electroless composite coating exhibited higher wear resistance and lower friction coefficient than Ni-P-SiC and Ni-P-graphite composite coatings. After annealing at 673 K for 2 h, the wear resistance of the Ni-P-CNT composite coating was improved. Carbon nanotube/copper matrix composites revealed a lower wear rate and friction coefficient compared with pure copper, and their wear rates and friction coefficients showed a decreasing trend with increasing volume fraction of CNTs within the range from 0 to 12 vol.% due to the effects of the reinforcement and reduced friction of CNTs. The favorable effects of CNTs on the tribological properties are attributed to improved mechanical properties and unique topological structure of the hollow nanotubes.     

Effects of silanization of C/C composites and grafting of h-BN fillers on the microstructure and interfacial properties of CVI-based C/C-BN composites

A low-density carbon/carbon (C/C) composite/silane coupling agent/hexagonal boron nitride (h-BN) hybrid reinforcement was prepared by grafting polyethyleneimine (PEI)-encapsulated modified h-BN fillers onto a carbon fiber surface using 3-aminopropyltriethoxysilane (APS) as the connection to improve the distribution uniformity of h-BN fillers in quasi-three-dimensional reinforcements and the interfacial properties between the fibers/pyrocarbon (PyC) in the C/C-BN composites obtained after densification by chemical vapor infiltration (CVI). The microstructure and chemical components of the hybrid reinforcement were investigated. The transmission electron microscopy (TEM) sample was prepared using a focused-ion beam (FIB) for the h-BN/PyC interfacial zone. The interlaminar shear strength (ILSS) and impact toughness were analyzed to inspect the composites’ interfacial properties. The results show that APS and h-BN are uniformly grafted on the fiber surface in the chopped fiber web inside the C/C composite without a density gradient, and agglomeration occurred and significantly increasing the fiber surface roughness. The highly ordered h-BN basal plane may affect the order degree of PyC near the h-BN/PyC interface. The addition of h-BN reduces the PyC texture near it, causing the annular cracks to disappear gradually. The lower PyC texture and the rougher fiber surface strengthen the interfacial bond of the fiber/matrix. Consequently, the ILSS strength of the C/C-BN composites first increases and then decreases as the h-BN filler content increases and is always higher than that of the C/C composite, while the addition of h-BN fillers weakens its impact toughness. When the h-BN content in the C/C-BN composite is 10 vol%, the ILSS of the C/C-BN composites was 15.6% higher than that of the C/C composites. However, when the h-BN content is excessive (15 vol%), the densely grafted h-BN will bridge each other, reducing the subsequent CVI densification efficiency to form a loose interface, causing a decrease in the shear strength.     

Ultra high thermal conductivity polymer composites

Epoxy composites based on vapor grown carbon fiber (VGCF) were fabricated and analyzed for room temperature thermophysical properties. An unprecedented high thermal conductivity of 695 W/m K for polymer matrix composites was obtained. The densities of all the composites are lower than 1.5 g/cc. In addition the high value of coefficient of thermal expansion (CTE) of the polymer material was largely reduced by the incorporation of VGCF. Also, unlike metal matrix composite (MMC), the epoxy composite has an electrically insulating surface. Based on the composite thermal conductivities, the room temperature thermal conductivity of VGCF, heat-treated at 2600°C, was estimated to be 1260 W/m K. Furthermore, the longitudinal CTE of the heat-treated VGCF was determined, for the first time, to be −1.5 ppm/K.     

Wear of carbon fiber reinforced carbon matrix composites: Study of abrasive,oxidative wear and influence of humidity

The wear of C/C composites has been studied using a subscale aircraft brake dynamometer linked with a mass spectrometer. A disc-on-disc configuration allowed for simulation of various aircraft landing energy conditions (12.5%, 25%, 50%, and 100% of normal landing energy of a Boeing 737 aircraft) performed at 50% and 90% relative humidity levels. The microstructure of composite brakes was altered by applying three different heat treatment temperatures: 1800, 2100, and 2400 °C, respectively. A mass spectrometer linked to an environmental chamber of the subscale dynamometer was utilized to measure the in situ CO₂ release during the wear tests. The relationships between microstructure, hardness of individual components of composites and wear performance at varied conditions are presented. Carbons obtained at higher heat treatment temperatures are most vulnerable to abrasive wear, while the less ordered carbons, typical for samples heat treated at lower temperatures, showed significant amount of oxidative wear. Oxidative wear was related to excessive heating of materials. Optimization of wear behavior of C/C composite is only possible by understanding the mechanisms of the microstructural changes of materials, corresponding mechanical properties and the nature of wear under various environmental conditions.     

Mechanical behavior of two-dimensional carbon/carbon composites with interfacial carbon layers

Effect of interfacial carbon layers on the mechanical properties and fracture behavior of two-dimensional carbon fiber fabrics reinforced carbon matrix composites were investigated. Phenolic resin reinforced with two-dimensional plain woven carbon fiber fabrics was used as starting materials for carbon/carbon composites and was prepared using vacuum bag hot pressing technique. In order to study the effect of interfacial bonding, a carbon layer was applied to the carbon fabrics in advance. The carbon layers were prepared using petroleum pitch with different concentrations as precursors. The experimental results indicate that the carbon/carbon composites with interfacial carbon layers possess higher fracture energy than that without carbon layers after carbonization at 1000°C. For a pitch concentration of 0.15 g/ml, the carbon/carbon composites have both higher flexural strength and fracture energy than composites without carbon layers. Both flexural strength and fracture energy increased for composites with and without carbon layers after graphitization. The amount of increase in fracture energy was more significant for composites with interfacial carbon layers. Results indicate that a suitable pitch concentration should be used in order to tailor the mechanical behavior of carbon/carbon composites with interfacial carbon layers.     

Fiber bundle push-out test and image-based finite element simulation for 3D carbon/carbon composites

The interfacial properties such as debond strength, fracture energy release rate in Mode-II and coefficient of friction play important roles in determining the mechanical properties and strength of carbon/carbon (C/C) composites. Push-out tests were conducted on 3D C/C composites and the experimental results were fitted to the shear lag model to determine these interfacial properties. X-ray tomography was used to explore the internal material structure of the composite. The fiber bundle and matrix interfaces were observed as being partially damaged in the tomographic images and the crack network was explored in detail. The tomographic images were also used to reconstruct a finite element (FE) mesh for simulating push-out tests. The interface of the fiber bundle and matrix in the FE mesh was represented by cohesive surfaces with frictional contact. The cohesive surface properties were obtained by matching FE results with the experimental results. The simulations had a good agreement with experiments and values of 0.75 for coefficient of friction, 2–5 N/mm² for debond stress, 1–4 N/mm² for clamping stress and 3–6 N/m for fracture energy release rate were obtained as interfacial parameters for the composite.     

Carbon fiber reinforced ceramic matrix composites with an oxidation resistant boron nitride interface coating

Toughening a ceramic in a ceramic matrix composite (CMC) depends on an ability of the composite to tolerate an accumulation of matrix cracks. When the reinforcement phase is carbon fiber, these cracks leave the fiber susceptible to destructive oxidation by ingress of air during high temperature exposure. Generally, a graphitic carbon interface coating is applied to carbon fibers because it provides for a weak bond between fiber and matrix that is required to promote toughening. This investigation seeks to utilize a BN coating instead of a C coating in order to promote oxidation resistance. Like graphitic carbon, BN is soft and easily cleavable. Preliminary observations that C/BN/SiC CMC's using Toray T300 carbon fibers were highly brittle and of low strength lead to a requirement of heat treating the fibers prior to the CVD of BN for toughened composites to be fabricated. It is likely heat treating removed reactive functionalities from the fiber surface to yield a weakly adhered and compliant interface.     

Effect of a Boron Nitride Interphase That Debonds between the Interphase and the Matrix in SiC/SiC Composites

Typically, the debonding and sliding interface enabling fiber pullout for SiC-fiber-reinforced SiC-matrix composites with BN-based interphases occurs between the fiber and the interphase. Recently, composites have been fabricated where interface debonding and sliding occur between the BN interphase and the matrix. This results in two major improvements in mechanical properties. First, significantly higher failure strains were attained due to the lower interfacial shear strength with no loss in ultimate strength properties of the composites. Second, significantly longer stress-rupture times at higher stresses were observed in air at 815°3C. In addition, no loss in mechanical properties was observed for composites that did not possess a thin carbon layer between the fiber and the interphase when subjected to burner-rig exposure. Two primary factors were hypothesized for the occurrence of debonding and sliding between the BN interphase and the SiC matrix: a weaker interface at the BN/matrix interface than the fiber/BN interface and a residual tensile/shear stress-state at the BN/matrix interface of melt-infiltrated composites. Also, the occurrence of outside debonding was believed to occur during composite fabrication, i.e., on cooldown after molten silicon infiltration.     

Comparative study of interphase evolution in polysiloxane resin-derived matrix containing carbon micro and nanofibers during thermal treatment

The work presents the results of research on composite materials made of silicon-containing polymer-derived ceramic matrix composites (PDC-Cs) and nanocomposites (PDC-NCs). Carbon micro and nanofibers (CFs and CNFs) were used as reinforcements. The interactions between carbon micro and nanofibers and polysiloxane matrix, as well as interphase evolution mechanism in composite samples during their heating to 1000 °C were studied. CF/resin and CNF/resin composites were prepared via liquid precursor infiltration process of unidirectionally aligned fibers. After heating to 700 °C–800 °C, decomposition of the resin in the presence of CNFs led to the formation of fiber/organic-inorganic composites with pseudo-plastic properties and improved oxidation resistance compared to as-prepared fiber/resin composites. The most favourable mechanical properties and oxidation resistance were obtained for composites and nanocomposites containing the maximum amount of carbon nanoparticles precipitated in the SiOC matrix during the heat treatment at 800 °C. The precipitated carbon phase improves fiber/matrix adhesion of composites.     

Fabrication of carbon/carbon composites by an electrified preform heating CVI method

Carbon/carbon composites are manufactured using the electrified preform producing directly heat CVI process. The preforms are prepared by laminating the carbon fiber felts with crossply reinforcement, and infiltrated with carbon using natural gas or propylene as a reactant, with nitrogen as diluent at atmospheric pressure. The relations between the resistivity of samples and infiltration time are determined under the operating conditions. The results indicate that the preforms have gained a high infiltration rate by this technology, and the samples have higher densities using natural gas rather than propylene. Their highest average bulk densities are up to 1.71 g/cm³ after the preforms of 1100×500×35 mm size have been densified for 80 h using natural gas. The carbon fibres in the preforms have not been damaged by this technology as yet, and the composites prepared have sufficiently high flexural properties. As the brake angular velocity is increased with the constant brake moment inertia and specific pressure, the average coefficient of friction for the composites prepared using natural gas is linearly and greatly decreased, but the variations of the brake moment inertia have a slight influence on the average coefficient of the friction when the brake angular velocity and specific pressure are kept constant. Their average thickness wear is 13×10⁻⁴ mm/surface per stop.     

碳/碳化硅摩阻复合材料的研究进展

碳/碳化硅是近年来发展起来的一种新型高性能陶瓷基摩阻材料,具有密度低,抗氧化性好,摩擦性能高且性能稳定等一系列优点,在高速列车、飞机和重型汽车等高能载制动领域具有广泛的应用前景.反应性熔体浸渗法是制备碳/碳化硅摩阻复合材料的有效途径.从碳/碳化硅摩阻复合材料的设计出发,深入分析了反应性熔体渗透过程的热力学条件,Si-C反应体系的基本特征以及动力学规律.针对短纤维模压和三维针刺等两种典型C/SiC复合材料的制备过程,对材料的微结构特征和摩擦磨损性能进行了系统论述.同时,对红外热成像、X射线透射和工业CT等先进工程检测方法在碳/碳化硅摩阻复合材料构件上的应用进行了分析.