Carbon/carbon-boron nitride composites with improved wear resistance compared to carbon/carbon

This paper describes the fabrication of a carbon fiber reinforced/carbon-boron nitride (C/C-BN) hybrid matrix composite for possible use in aircraft brakes. These composites were fabricated via liquid infiltration of a liquid crystalline borazine oligomer into a low-density carbon fiber/carbon matrix (C/C) composite. The friction and wear properties of the C/C-BN were explored over the entire energy spectrum for aircraft braking using an inertial brake dynamometer. The C/C-BN composites with densities of 1.55 g/cc displayed wear rates 50% lower than values observed with C/C samples with densities of approximately 1.75-1.8 g/cc. This includes the near elimination of wear from 300 to 600 kJ/kg, which represents the normal landing regime for aircraft brakes. This encouraging behavior is attributed in part to the improved oxidation resistance of the BN at high energy levels and the ability of the BN to facilitate formation of a stable wear film at lower energy levels. The coefficient of friction, while being slightly lower than the values for C/C, appeared much less sensitive to changes in energy level.     

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.     

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.     

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.     

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.     

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.     

Fabrication and Properties of Ceramic Composites with a Boron Nitride Matrix

Boron nitride (BN) matrix composites reinforced by a number of different ceramic fibers have been prepared using a low-viscosity, borazine oligomer which converts in very high yield to a stable BN matrix when heated to 1200°C. Fibers including Nicalon (SiC), FP (A1₂O₃), Sumica and Nextel 440 (Al₂O₃-SiO₂) were evaluated. The Nicalon/BN and Sumica/BN composites displayed good flexural strengths of 380 and 420 MPa, respectively, and modulus values in both cases of 80 GPa. On the other hand, FP/BN and Nextel/BN composites exhibited very brittle behavior. Nicalon fiber with a carbon coating as a buffer barrier improved the strength by 30%, with a large amount of fiber pullout from the BN matrix. In all cases except for Nicalon, the composites showed low dielectric constant and loss.     

Microstructure and mechanical properties of Si3N4f/BN composites with BN interphase prepared by chemical vapor deposition of borazine

The boron nitride (BN) interphase of silicon nitride (Si₃N₄) fiber-reinforced BN matrix (Si₃N_4f/BN) composites was prepared by chemical vapor deposition (CVD) of liquid borazine, and the microstructure, growth kinetics and crystallinity of the BN coating were examined. The effects of coating thickness on the mechanical strength and fiber/matrix interfacial bonding strength of the composites were then investigated. The CVD BN coating plays a key role in weakening the interfacial bonding condition that improves the mechanical properties of the composites. The layering structure of the BN coating promotes crack propagation within the coating, which leads to a variety of toughening mechanisms including crack deflection, fiber bridging and fiber pull out. Single-fiber push-out experiments were performed to quantify the fiber/matrix bonding strength with different coating thicknesses. The physical bonding strength due to thermal mismatch was discussed.     

Nearly stoichiometric BN fiber by curing and thermolysis of a novel poly[(alkylamino)borazine]

Boron nitride (BN) fiber with a composition of BN_1.09 was fabricated by curing and thermolysis of a novel poly[(alkylamino)borazine]. The processes have been studied by a combination of gel-content test, TGA, elemental analysis, IR, XPS, XRD, SEM and TEM. The results show that curing made polymer fiber infusible and resulted in a significant improvement of ceramic yield from 53.2 wt% to 73.8 wt% at 1000 °C. Moreover, pyrolysis in NH₃ at 1200 °C generated a nearly stoichiometric BN without carbonaceous impurities while in Ar led to a BNC material with carbon content of 6.13 wt%. The obtained amorphous BN fiber with a diameter of 13 μm displayed a tensile strength of approximately 600 MPa. Furthermore, the BN fiber illustrated good oxidation resistance in air.     

Thermophysical properties of carbon/carbon composites and physical mechanism of thermal expansion and thermal conductivity

Five different carbon/carbon composites (C/C) have been prepared and their thermophysical properties studied. These were three needled carbon felts impregnated with pyrocarbons (PyC) of different microstructures, chopped fibers/resin carbon + PyC, and carbon cloth/PyC. The results show that the X-Y direction thermal expansion coefficient (CTE) is negative in the range 0-100 °C with values ranging from −0.29 to −0.85 × 10⁻⁶/K. In the range 0-900 °C, their CTE is also very low, and the CTE vs. T curves have almost the same slope. In the same temperature range composites prepared using chopped fibers show the smallest CTE values and those using the felts show the highest. The microstructure of the PyC has no obvious effect on the CTE for composites with the same preform architecture. Their expansion is mainly caused by atomic vibration, pore shrinkage and volatilization of water. However, the PyC structure has a large effect on thermal conductivity (TC) with rough laminar PyC giving the highest value and isotropic PyC giving the lowest. All five composites have a high TC, and values in the X-Y direction (25.6-174 W/m K) are much larger than in the Z direction (3.5-50 W/m K). Heat transmission in these composites is by phonon interaction and is related to the preform and PyC structures.     

Thermal diffusivity of three-dimensional needled C/SiC-TaC composites

Three-dimensional needled carbon fiber reinforced SiC-TaC composites were prepared by combination of slurry infiltration and reactive melt infiltration. The thermal diffusivity of the composites with different TaC contents was characterized in the temperature range from room temperature to 1400 °C. The results revealed that the temperature dependent thermal diffusivity behavior was independent on TaC content, while the thermal diffusivity values of the composites were influenced by their microstructures. A model based on lattice vibration and microstructure was used to discuss the thermal diffusivity behavior of the C/SiC-TaC composites.     

Fabrication and characterization of random chopped fiber reinforced reaction bonded silicon carbide composite

This paper deals with the microstructure and mechanical properties of reaction bonded silicon carbide reinforced with random chopped carbon fibers of 3 mm length. The composites were fabricated by dispersing chopped carbon fibers into bimodal SiC/C suspension, forming green body through slip casting, and then reaction sintering at 1700 °C. The effect of the chopped fiber fraction on microstructure and mechanical properties was evaluated. A significant increase of fracture toughness was obtained as the carbon fiber fraction approaches 30 vol.%. The chopped fibers had reacted with liquid silicon during reaction sintering, so little fiber pullout was observed. Crack deflection and bridging is the predominant mechanism for the composite toughening.     

Thermal behaviour of a series of poly[B-(methylamino)borazine] for the preparation of boron nitride fibers

The thermal behaviour of a series of poly[B-(methylamino)borazine] prepared at various temperatures ranging from 140 to 200 °C is studied in the present paper as potential BN fiber precursors. It was shown that the softening capability of poly[B-(methylamino)borazine] can be tailored by controlling the temperature at which polymers were prepared to achieve melt-spinning and produce high quality green fibers. Thus as-spun fibers could be next converted into boron nitride fibers using ammonia (25–1000 °C) and nitrogen (25–1800 °C) atmospheres. The quality of boron nitride fibers was shown to depend on the first part of the pyrolysis step (25 and 1000 °C; ammonia atmosphere) in which the great majority of the weight loss necessary for boron nitride production occurs. Ideal poly[B-(methylamino)borazine] as BN fiber precursors are those prepared between 170 and 180 °C. They display appropriate melt-spinnability and ceramic conversion capability.     

Silicon nitride/boron nitride ceramic composites fabricated by reactive pressureless sintering

Using Si and BN powders as raw materials, silicon nitride/hexagonal boron nitride (Si₃N₄/BN) ceramic composites were fabricated at a relatively low temperature of 1450 °C by using the reaction bonding technology. The density and the nitridation rate, as well as the dimensional changes of the specimens before and after nitridation were discussed based on weight and dimension measurements. Phase analysis by X-ray diffraction (XRD) indicated that BN could promote the nitridation process of silicon powder. Morphologies of the fracture surfaces observed by scanning electron microscopy (SEM) revealed the fracture mode for Si₃N₄/BN ceramic composites to be intergranular. The flexural strength and Young's modulus decreased with the increasing BN content. The reaction-bonded Si₃N₄/BN ceramic composites showed better machinability compared with RBSN ceramics without BN addition.     

Effect of BN or B4C content on physical and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin

Plasma treatment was used to improve the surface roughness of copper foil. The copper-clad laminates reinforced with carbon fiber, boron nitride (BN), or boron carbide (B₄C), and epoxy resin were prepared by hot pressing. The effect of BN or B₄C content on the physical properties and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin were studied. The resulting copper-clad laminate exhibited desirable properties, such as dielectric constant, peel strength, oxygen index, and arc resistance, which were influenced by the concentration of BN or B₄C particles. Additionally, the wear and friction properties of the laminate were evaluated, revealing the effects of load, sliding speed, and particle content on weight loss, specific wear rate, and coefficient of friction. SEM analysis of worn surfaces provided insight into the stages of wear, highlighting the importance of an oxide layer in reducing wear and protecting the copper surface.     

Microstructure observation and analysis of 3D carbon fiber reinforced SiC-based composites fabricated through filler enhanced polymer infiltration and pyrolysis

3D C/SiC-BN composites were fabricated by filler enhanced polymer infiltration and pyrolysis (FE-PIP) through in situ conversion of active filler boron into h-BN in the high temperature treatment process. The bending strengths and microstructures of composites were studied here. Interphase layers deposited on the fiber surfaces can prevent the strong bonding between fiber reinforcements and composite matrix and repair the defects on the fiber surface, which can improve the bending strength and toughness of composites. The bending stress of C/SiC-BN composites without interphase layer is about 170 MPa while those of composites with PyC or PyC/SiC interphase layers are higher than 300 MPa. Some large pores were left in the interwoven zones while intra-bundle zones were relatively dense, only a small amount of micro-pores could be observed. It could also be concluded that the length of pulled-out fibers was much longer and the pulled-out fiber surface was smoother when interphase layers were deposited. Because the matrix derived from the pyrolysis of slurries adheres to the fiber bundles, some phases with layered structures could be observed in the matrix near the reinforcements. The microstructure evolution of 3D fiber reinforced ceramic matrix composites were also analyzed in this work based on the observation of both 3D C/SiC-BN composites and 3D C/SiC composites fabricated by FE-PIP, where boron and SiC particles were applied as active fillers and inert fillers respectively.     

Novel processable precursor for BN by the polymer-derived ceramics route

Novel precursors polymerized from (alkylamino)borazines (AAB) were synthesized and transformation of processable poly-AAB to boron nitride (BN) was researched. The AAB monomers of the type (BNH)₃(NHR)₃ were synthesized via ammolysis of 2,4,6-trichloroborazine (TCB) with different propylamines under mild conditions. The specially designed monomers served as molecular precursors for BN by the polymer-derived ceramics route. The processability of the polymeric precursors varied with propylamino-groups of AAB linked with boron atoms on (BNH)₃. The good processability of the poly[2,4,6-tris(iso-propylamino)borazine] (PTPⁱAB) was proven by melt-spinning it into polymer fiber. Furthermore, the PTPⁱAB gave a ceramic yield of about 53 wt% in Ar at 1200 °C by TGA. Based on FTIR, Raman, XRD, XPS and elemental analysis, the pyrolytic product of PTPⁱAB showed a composition of BN_1.07. In addition, the BN illustrated excellent oxygen resistance in air.     

Fabrication and characteristic of non-oxide fiber tow reinforced silicon nitride matrix composites by low temperature CVI process

Non-oxide fiber tow reinforced silicon nitride matrix composite was fabricated by low temperature CVI process with PyC as interphase. The tensile strength of the C and SiC fiber tow composites were 547 MPa and 740 MPa, respectively. The difference in tensile strength was analyzed based on the length, amount of pull-out fiber and also interface bonding. The infiltration uniformity of CVI silicon nitride (SiN) matrix within SiC fiber tow was comparable with that of CVI SiC matrix. These results suggested that the low temperature CVI process is suitable for the fabrication of fiber reinforced SiN matrix composites with proper interface bonding and high strength.     

Fatigue of three advanced SiC/SiC ceramic matrix composites at 1200°C in air and in steam

High‐temperature mechanical properties and tension‐tension fatigue behavior of three advanced SiC/SiC composites are discussed. The effects of steam on high‐temperature fatigue performance of the ceramic‐matrix composites are evaluated. The three composites consist of a SiC matrix reinforced with laminated, woven SiC (Hi‐Nicalon?) fibers. Composite 1 was processed by chemical vapor infiltration (CVI) of SiC into the Hi‐Nicalon? fiber preforms coated with boron nitride (BN) fiber coating. Composite 2 had an oxidation inhibited matrix consisting of alternating layers of silicon carbide and boron carbide and was also processed by CVI. Fiber preforms had pyrolytic carbon fiber coating with boron carbon overlay applied. Composite 3 had a melt‐infiltrated (MI) matrix consolidated by combining CVI‐SiC with SiC particulate slurry and molten silicon infiltration. Fiber preforms had a CVI BN fiber coating applied. Tensile stress‐strain behavior of the three composites was investigated and the tensile properties measured at 1200°C. Tension‐tension fatigue behavior was studied for fatigue stresses ranging from 80 to 160 MPa in air and from 60 to 140 MPa in steam. Fatigue run‐out was defined as 2 × 10⁵ cycles. Presence of steam significantly degraded the fatigue performance of the CVI SiC/SiC composite 1 and of the MI SiC/SiC composite 3, but had little influence on the fatigue performance of the SiC/SiC composite 2 with the oxidation inhibited matrix. The retained tensile properties of all specimens that achieved fatigue run‐out were characterized. Composite microstructure, as well as damage and failure mechanisms were investigated.     

Influence of hBN content on mechanical and tribological properties of Si3N4/BN ceramic composites

Silicon nitride materials containing 1–5 wt% of hexagonal boron nitride (micro-sized or nano-sized) were prepared by hot-isostatic pressing at 1700 °C for 3 h. Effect of hBN content on microstructure, mechanical and tribological properties has been investigated. As expected, the increase of hBN content resulted in a sharp decrease of hardness, elastic modulus and bending strength of Si₃N₄/BN composites. In addition, the fracture toughness of Si₃N₄/micro BN composites was enhanced comparing to monolithic Si₃N₄ because of toughening mechanisms in the form of crack deflection, crack branching and pullout of large BN platelets. The friction coefficient was not influenced by BN addition to Si₃N₄/BN ceramics. An improvement of wear resistance (one order of magnitude) was observed when the micro hBN powder was added to Si₃N₄ matrix. Mechanical wear (micro-failure) and humidity-driven tribochemical reaction were found as main wear mechanisms in all studied materials.