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.     

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.     

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.     

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.     

Investigation of non-isothermal crystallization,dynamic mechanical and dielectric properties of poly(ether-ketone) matrix composites

ABSTRACT

Poly(ether-ketone)/hexagonal boron nitride (h-BN) composites reinforced with micrometer-sized h-BN particles were investigated. The composites exhibited glass transition temperature (T_g) and thermal stability over 160°C and 560°C, respectively. The melting point and peak crystallization temperatures of the composites decreased up to 17°C and 12°C, respectively. The linear CTE of the composites decreased both below and above the T_g. The storage modulus increased with increasing h-BN content at all temperatures (50–250°C). The composites possessed excellent dielectric properties with insignificant dispersion with increasing frequency. Thus, resultant composites are promising candidates for the printed circuit boards/electronic substrates.     

Influence of h-BN as additive on microstructure and oxidation mechanism of C/C-SiC composite

Due to the favorable self-healing performance, hexagonal boron nitride (h-BN) as additive in the matrix can significantly influence the oxidation behavior and the kinetic characteristics of C/C-SiC composites. In this work, C/C-SiC composites modified by h-BN (C/C-BN-SiC) were prepared by low-temperature compression molding (LTCM), pyrolysis and liquid silicon infiltration (LSI). Microstructure, oxidation behavior and kinetic characteristics of the C/C-BN-SiC composites were investigated compared with the C/C-SiC composite. Because h-BN is non-wetted by liquid silicon, the h-BN flakes in the matrix can obstruct and prolong the flow path of silicon, and protect the carbon fibers from corrosion to a certain extent. The oxidation kinetics of composites occur in low and high temperature domains, with different oxidation-controlling mechanisms, and the addition of h-BN can hinder the inward diffusion and lead to the decline of carbon recession and apparent activation energy.     

Synthesis and characterization of nanocrystaline hexagonal boron nitride powders: XRD and luminescence properties

Nanocrystalline hexagonal boron nitride powders (h-BN) were synthesized from urea and boric acid followed by pirolysis and subsequent heat treatment in nitrogen atmosphere. Materials have been analyzed by means of X-ray diffraction, Photoluminescence and Field emission electron microscopy methods. Obtained results show that starting h-BN powder, synthesized at 750 °C, is composed of ~11 layer crystallites with average crystallite thickness and crystallite lateral size of 3.94 and 10.4 nm, respectively. A broad emission and intense luminescence intensity were observed due to the large atomic disorder. Higher annealing temperature increases crystallite size and turbostratic h-BN transforms to well crystallized h-BN at 1500 °C.     

Microstructure and damage evolution of SiCf/PyC/SiC and SiCf/BN/SiC mini-composites: A synchrotron X-ray computed microtomography study

SiC_f/PyC/SiC and SiC_f/BN/SiC mini-composites comprising single tow SiC fibre-reinforced SiC with chemical vapor deposited PyC or BN interface layers are fabricated. The microstructure evolutions of the mini-composite samples as the oxidation temperature increases (oxidation at 1000, 1200, 1400, and 1600?°C in air for 2?h) are observed by scanning electron microscopy, energy dispersive spectrometry, and X-ray diffraction characterization methods. The damage evolution for each component of the as-fabricated SiC_f/SiC composites (SiC fibre, PyC/BN interface, SiC matrix, and mesophase) is mapped as a three-dimensional (3D) image and quantified with X-ray computed tomography. The mechanical performance of the composites is investigated via tensile tests.The results reveal that tensile failure occurs after the delamination and fibre pull-out in the SiC_f/PyC/SiC composites due to the volatilization of the PyC interface at high temperatures in the air environment. Meanwhile, the gaps between the fibres and matrix lead to rapid oxidation and crack propagation from the SiC matrix to SiC fibre, resulting in the failure of the SiC_f/PyC/SiC composites as the oxidation temperature increases to 1600?°C. On the other hand, the oxidation products of B₂O₃ molten compounds (reacted from the BN interface) fill up the fracture, cracks, and voids in the SiC matrix, providing excellent strength retention at elevated oxidation temperatures. Moreover, under the protection of B₂O₃, the SiC_f/BN/SiC mini-composites show a nearly intact microstructure of the SiC fibre, a low void growth rate from the matrix to fibre, and inhibition of new void formation and the SiO₂ grain growth from room to high temperatures. This work provides guidance for predicting the service life of SiC_f/PyC/SiC and SiC_f/BN/SiC composite materials, and is fundamental for establishing multiscale damage models on a local scale.     

Synthesis of highly purified and crystallized h-BN using calcium-assisted carbothermal reduction nitridation

Highly purified and crystallized hexagonal boron nitride (h-BN) powder is suitable as thermally conductive filler in resins. To obtain h-BN powder with large particle size, as well as high purity and crystallinity, high-temperature heat treatment over 1800°C in a N₂ gas atmosphere is effective. The carbothermal reduction nitridation (CRN) involves the carbothermic reduction of boric oxide in a N₂ gas atmosphere. In CRN using a CaO promoter, h-BN particles with high crystallinity can be obtained by a simple heat treatment process. CaO prevents the evaporation of boron oxide and aids in h-BN particle growth at high temperatures. However, CaB₆ is formed as byproduct or impurity when CRN using the CaO promoter is performed at temperatures higher than 1800°C. In this study, the relationship between the products and the reaction temperature was clarified via thermodynamic considerations and experimentation. The results clarified the ideal reaction process of CRN using a CaO promoter to obtain highly purified and crystallized h-BN powder.     

Mechanical properties of SiCf/SiC composites with alternating PyC/BN multilayer interfaces

Alternating pyrolytic carbon/boron nitride (PyC/BN)_n multilayer coatings were applied to the KD–II silicon carbide (SiC) fibres by chemical vapour deposition technique to fabricate continuous SiC fibre-reinforced SiC matrix (SiC_f/SiC) composites with improved flexural strength and fracture toughness. Three-dimensional SiC_f/SiC composites with different interfaces were fabricated by polymer infiltration and pyrolysis process. The microstructure of the coating was characterised by scanning electron microscopy, X–photoelectron spectroscopy and transmission electron microscopy. The interfacial shear strength was determined by the single-fibre push-out test. Single-edge notched beam (SENB) test and three-point bending test were used to evaluate the influence of multilayer interfaces on the mechanical properties of SiC_f/SiC composites. The results indicated that the (PyC/BN)_n multilayer interface led to optimum flexural strength and fracture toughness of 566.0?MPa and 21.5?MPa?m^1/2, respectively, thus the fracture toughness of the composites was significantly improved.     

High-temperature flexural strength of I-CVI processed Cf/SiC composites with variable interphases

The effect of single-layer pyrocarbon (PyC) and multilayered (PyC/SiC)_n=4 interphases on the flexural strength of un-coated and SiC seal-coated stitched 2D carbon fiber reinforced silicon carbide (C_f/SiC) composites was investigated. The composites were prepared by I-CVI process. Flexural strength of the composites was measured at 1200 °C in air atmosphere. It was observed that irrespective of the type of interphase, the seal coated samples showed a higher value of flexural strength as compared to the uncoated samples. The flexural strength of 470 ± 12 MPa was observed for the seal coated C_f/SiC composite samples with multilayered interphase. The seal coated samples with single layer PyC interphase showed flexural strength of 370 ± 20 MPa. The fractured surfaces of tested samples were analyzed in detail to study the fracture phenomena. Based on microstructure-property relations, a mechanism has been proposed for the increase of flexural properties of C_f/SiC composites having multilayered interphase.     

The influence of polyelectrolyte on the synthesis of B4C/BN nanocomposite powders via sol-gel method

In the present study, B₄C-BN nanocomposite powders were synthesized by using the sol-gel method. To investigate the effects of polyelectrolyte on phase content, particle size, and final morphology of synthesized powders different amounts of ammonium polycarboxylate were used as a gel dispersing agent and a nitrogen source. Highly crystalline, sub-micron/micron-sized boron carbide particles with varying morphologies including polyhedral-equiaxed, belt-like, needle-like, and complex-shaped hierarchical structures were produced from the polymeric gel containing glycerine, tartaric acid, and citric acid as carbon sources, and boric acid as boron source. With the addition of ammonium polycarboxylate as a polymeric gel network modifier, nanocomposite powders containing micron-sized polyhedral-equiaxed boron carbide particles and boron nitride nanoflakes were obtained. The results indicated that the particles dimensions, crystallinity, and B₄C to BN phase ratio of the synthesized powders are directly related to the preliminary formation of borate-ammonium and/or amine complexes in the polymeric gel. The SEM inspections revealed that the size of boron carbide particles tends to increase from 2 μm up to 40 μm as a function of ammonium polycarboxylate content. It was also observed that the average size and thickness of boron nitride nanoflakes within the range of 80 nm to 3 μm and 10–150 nm, respectively. B₄C/BN nanocomposite powders were synthesized with up to 32% BN content using a 43 wt% ammonium polycarboxylate additive.     

High-temperature atomically laminated materials: The toughening components of ceramic matrix composites

The atomically laminated materials with high temperature resistance, including graphite, hexagonal boron nitride (h-BN) and MAX phases, have special mechanical performance compared to isotropic materials. The intrinsic mechanical responses of these layered structures can play an important role in strengthening and toughening ceramic matrix composites. In this review, the synthesis processes and applications of pyrolytic carbon (PyC) interphase, graphite nanoplates (GNPs), h-BN interphase, and h-BN nanoplates (BNNPs) and MAX phases are summarized. Besides, this review also analyzes the differences between the graphite-like structure and the MAX phase structure, in terms of modulus, toughness, anisotropy, and toughening mechanisms. These differences are based on their crystal structures. Finally, we look forward to the future development direction of high-temperature atomically laminated materials for toughening applications.     

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.     

Siliconization elimination for SiC coated C/C composites by a pyrolytic carbon coating and the consequent improvement of the mechanical property and oxidation resistances

Carbon/carbon (C/C) composites have a wide application as the thermal structure materials because of their excellent properties at high temperatures. However, C/C composites are easily oxidized in oxygen-containing environment, which limits their potential applications to a great degree. Silicon carbide (SiC) ceramic coating fabricated via pack cementation (PC) was considered as an effective way to protect C/C composites against oxidation. But the mechanical properties of C/C composites were severely damaged due to chemical reaction between the molten silicon and C/C substrate during the preparation of SiC coating by PC. In order to eliminate the siliconization erosion, a pyrolytic carbon (PyC) coating was pre-prepared on C/C composites by the chemical vapor infiltration (CVI) prior to the fabrication of SiC coating. Due to the retardation effect of PyC coating on siliconization erosion, the flexural strength retention of the SiC coated C/C composites with PyC coating increased from 46.27 % to 107.95 % compared with the specimen without PyC coating. Furthermore, the presence of homogeneous and defect-free PyC coating was beneficial to fabricate a compact SiC coating without silicon phase by sufficiently reacting with molten silicon during PC. Therefore, the SiC coated C/C composites with PyC coating had better oxidation resistances under dynamic (between room temperature and 1773 K) and static conditions in air at different temperatures (1773?1973 K).     

Influence of sintering temperature on the crystallization and mechanical properties of BN-MAS composites

A type of boron nitride–magnesium aluminum silicate (BN-MAS) composite ceramics was fabricated by hot-press sintering at different sintering temperatures. The relationship between the sintering temperature and microstructure was investigated by analyzing the interaction between hexagonal boron nitride (h-BN) and the MAS phase. The main MAS phase in the composite ceramics is the α-cordierite phase at a sintering temperature of 1300°C. At temperatures above 1400°C, the inhibitory effect of h-BN on the crystallization of the MAS system is significant, and MAS mainly exists in the form of an amorphous phase. The composite sintered at 1700°C exhibited the highest bending strength of 218MPa. h-BN and MAS were co-enhanced. MAS can be used as an effective liquid-phase sintering aid to assist in the sintering of h-BN, whereas h-BN can absorb the fracture energy of the composite ceramics through the pull-out and bridging effect of the particles.     

High temperature flexural strength,microstructure, phase evolution and anti-oxidation mechanism of Al-coated carbon fiber/boron phenolic resin ceramizable composite modified with TiB2 and B4C

Carbon fiber/phenolic resin composites (CF/Ph) have attracted great interests in the field of thermal protection materials for their characteristics of high specific strength and easy manufacturing. However, CF/Ph are inherently susceptible to oxidation failure at elevated temperatures. In this study, a novel Al-coated carbon fiber/boron phenolic resin ceramizable composite modified with TiB₂ and B₄C was fabricated by an impregnating and compression molding route. Thermal stability, flexural strength, microstructure and phase evolution of the resulting ceramizable composite were studied. The residue yield at 1400 °C and flexural strength after treated at 1400 °C for 15min was 90.4% and 53.1 MPa, respectively, which was increased by 15.9% and 532.1% than that without ceramizable fillers. Surface defects generated by matrix pyrolysis were well healed, and PyC and carbon fibers were covered with dense ceramic layers while the fracture surface was covered with relatively continuous ceramic layers without visible pores. Multiphase ceramics composed of TiB₂, TiO₂, TiC and PyC were identified. Furthermore, oxidation failure and anti-oxidation mechanism was revealed based on the aforementioned characterizations and thermodynamic calculation results. Oxidation resistance got enhanced markedly for synergistic effects of oxygen consuming, carbon fixation, oxygen barrier and endothermic effect, which were derived from ceramization reactions between TiB₂, B₄C, O₂, Al and PyC.     

Thermal properties and formation mechanism of h‐BN nanoneedles synthesized via carbothermic reduction reaction

Hexagonal boron nitride (BN) was synthesized through the carbothermic reduction reaction (CRR) of boric acid using lactose as a carbon source under the nitrogen atmosphere at 1500^°C for 3 hours. The boron/carbon (B/C) molar ratio was controlled during the CRR, and the produced samples were investigated by XRD diffraction pattern, FTIR analysis, and Raman spectra. Boron carbide (B₄C) was formed in samples that have a higher carbon content, in addition to boron nitride. While boron nitride pure sample was produced from lower carbon content samples. Formation of B₄C was found to depend on the B/C molar ratio. The morphology of the produced powder was also investigated by SEM and TEM, which revealed that the samples consist of nanoneedles of BN and hexagonal particles of B₄C. The vapor‐solid (VS) reaction mechanism was processed greatly with increasing boron amount, producing boron nitride nanoneedles, which compete with the liquid‐solid (LS) reaction mechanism. The physicochemical properties of the produced samples were studied by DTA, UV, PL, and AC impedance measurements, and revealed that the samples are promising to many proper applications.     

Mechanical,dielectric and thermal properties of porous boron nitride/silicon oxynitride ceramic composites prepared by pressureless sintering

Porous boron nitride/silicon oxynitride (BN/Si₂N₂O) composites were fabricated by pressureless sintering at 1650 °C with Li₂O as sintering aid. The influence of Li₂O and hexagonal boron nitride (h-BN) contents on phase, microstructure, mechanical, dielectric and thermal properties of the resulting porous BN/Si₂N₂O composites was investigated. Increasing Li₂O content facilitated densification and decomposition of Si₂N₂O into Si₃N₄. The apparent porosity of the composites increases with the h-BN content increases and Si₂N₂O grain growth was restrained by the dispersed h-BN particles. The dielectric properties and thermal conductivities (TC) were affected mainly by porosity. Porous BN/Si₂N₂O ceramic composites with 4 mol% Li₂O and 25 mol% BN exhibit both low dielectric constant (3.83) and dielectric loss tangent (0.008) with good mechanical and thermal performance, suggesting possible use as high-temperature structural/functional materials.     

可加工氮化硼系复相陶瓷的研究发展现状和发展趋势以及应用现状分析

先进陶瓷材料具有较高的力学性能,以及较高的抗高温氧化性能等。但是先进陶瓷材料由于硬度较高、可加工性能较差,导致陶瓷材料的机械加工成本较高,所以限制了陶瓷材料的广泛应用。为了改善和提高陶瓷材料的可加工性能,向陶瓷基体中加入六方氮化硼形成可加工氮化硼系复相陶瓷。可加工氮化硼系复相陶瓷具有较高的力学性能和优良的可加工性能,氮化硼系复相陶瓷可以进行机械加工。目前研究和开发的可加工氮化硼系复相陶瓷主要包括:Al_2O_3/BN复相陶瓷,ZrO_2/BN复相陶瓷,SiC/BN复相陶瓷,Si_3N_4/BN复相陶瓷,AlN/BN复相陶瓷等。目前可加工氮化硼系复相陶瓷的研究主要集中在氮化硼系复相陶瓷的制备工艺,力学性能,可加工性能,抗热震性能,抗高温氧化性能等。本文主要叙述可加工氮化硼系复相陶瓷的制备工艺,力学性能和可加工性能,抗热震性能,抗高温氧化性能等。并叙述可加工氮化硼系复相陶瓷的研究发展现状和发展趋势,并对可加工氮化硼系复相陶瓷的未来发展趋势进行分析和预测。