A Si–SiC oxidation protective coating for carbon/carbon composites prepared by a two-step pack cementation

To prevent carbon/carbon (C/C) composites from oxidation, a Si–SiC coating has been prepared by a two-step pack cementation technique. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis show that the coating obtained by the first step pack cementation is a porous β-SiC structure, and a dense structure consisting α-SiC, β-SiC and Si is obtained after heat-treatment by the second step pack cementation. By energy dispersive spectroscopy (EDS) analysis, a gradient C–SiC transition layer can be formed at the C/C-coating interface. The as-received coating has excellent oxidation protection ability and can protect C/C composites from oxidation for 166 h at 1773 K in air. The weigh loss of the coated C/C is due to the formation of bubble holes on the coating surface and through-coating cracks in the coating.     

Effect of La2O3 addition on long-term oxidation kinetics of ZrB2–SiC and HfB2–SiC ultra-high temperature ceramics

Long-term oxidation kinetics of SiC-reinforced UHTCs and La₂O₃-doped UHTCs over an intermediate temperature range (1400–1600 °C) reveal partially protective behavior for the former characterized by an oxidation kinetic exponent 1 < n < 2. In addition, unstable oxidation behavior was observed in HfB₂-based UHTCs due to the presence of SiC agglomerates. On the other hand, La₂O₃-doped UHTCs were found to be protective over the whole temperature range studied (n = 2), in particular at 1600 °C, where oxidation kinetic exponents as high as 8 were observed as a consequence of formation of new oxidation protective particles, MeO_xC_y, where Me is Zr, Hf or Si. Adsorption of oxygen-containing species formed protective MeO_xC_y phases, which enhanced the thermal stability of the oxide scale as well as providing protection against oxidation for long exposure times at 1600 °C.     

Influence of graphite nano-flakes on densification and mechanical properties of hot-pressed ZrB2–SiC composite

Hot pressed monolithic ZrB₂ ceramic (Z), ZrB₂–20 vol% SiC composite (ZS₂₀) and ZrB₂–20 vol% SiC–10 vol% nano-graphite composite (ZS₂₀G_n10) were investigated to determine the influence of graphite nano-flakes on the sintering process, microstructure, and mechanical properties (Vickers hardness and fracture toughness) of ZrB₂–SiC composites. Hot pressing at 1850 °C for 60 min under 20 MPa resulted in a fully dense ZS₂₀G_n10 composite (relative density: 99.6%). The results disclosed that the grain growth of ZrB₂ matrix was efficiently hindered by SiC particles as well as graphite nano-flakes. The fracture toughness of ZS₂₀G_n10 composite (7.1 MPa m^1/2) was essentially improved by incorporating the reinforcements into the ZrB₂ matrix, which was greater than that of Z ceramic (1.8 MPa m^1/2) and ZS₂₀ composite (3.8 MPa m^1/2). The fractographical observations revealed that some graphite nano-flakes were kept in the ZS₂₀G_n10 microstructure, besides SiC grains, which led to toughening of the composite through graphite nano-flakes pull out. Other toughening mechanisms such as crack deflection and branching as well as crack bridging, due to the thermal residual stresses in the interfaces, were also observed in the polished surface.     

High-temperature oxidation resistance of spent MoSi2 modified ZrB2–SiC–MoSi2 coatings prepared by spark plasma sintering

The spent MoSi₂ modified ZrB₂–SiC–MoSi₂ coatings were prepared on carbon matrixes by spark plasma sintering. A continuous metallurgical bonding was formed at the interface between the coating and matrix, and no obvious defects such as pores and cracks were observed inside. The effects of spent MoSi₂ content and trace doping in the spent powder on the oxidation behavior of the coatings in air at 1700 °C were investigated. During the active oxidation stage, the spent MoSi₂ promoted the densification of the coating and enhanced the structural oxygen barrier properties. With the increase of service time, during the inert oxidation stage, doping an appropriate amount of spent MoSi₂ helped to increase the fluidity of the rich-SiO₂ protective layer so that the Zr oxides fully dispersed in the generated Zr–B–Si–O–Al multiphase glass layer, which could impede the penetration of oxygen and enhance the oxidation protection efficiency. However, excessive spent MoSi₂ exacerbated the volatilization of gas by-products, forming pores and cracks in the glass layer and rising the oxidation loss. When the content of spent MoSi₂ was 20 vol%, the glass layer is dense and uniform, with few defects and the best oxygen resistance property. Moreover, compared with commercial powders, spent MoSi₂ contained Al₂O₃ and SiO₂. Al₂O₃ had an excellent modification effect, while SiO₂ glass can promote liquid phase sintering and seal the defects in the coatings. By adding spent MoSi₂, the modified ZrB₂–SiC–MoSi₂ composite coatings could inhibit the formation of defects and improve the dynamic stability of the coatings effectively.     

A ZrB2–SiC/SiC oxidation protective dual-layer coating for carbon/carbon composites

In order to improve the oxidation resistance of C/C composites, a ZrB₂–SiC/SiC oxidation protective dual-layer coating was prepared by a pack cementation combined with the slurry paste method. The phase and microstructure of the coating were characterised by X-ray diffraction, scanning electron microscope and energy-dispersive spectrometer analyses. The anti-oxidation and thermal shock resistance of the coating were also investigated. It was found that the ZrB₂–SiC/SiC coating could effectively improve the oxidation resistance of the C/C composites. The weight loss of the coated samples was only 1.8% after oxidation at 1773?K for 18?h in air. The coating endured 20 thermal shock cycles between 1773?K and room temperature with only 4.6% weight loss.     

Effect of functionalised core–shell microgels prepared by emulsion polymerisation on acrylic coatings properties

The influence of hydroxyl-functionalised acrylic core–shell microgels incorporated into a solvent-borne acrylic binder system on the properties of coatings is described in this paper. Our approach has been to show the usefulness of prepared functionalised microgels as coating modifiers. This subject was shown to be connected with the selection of an appropriate solvent with good affinity for microgels and the film-forming polymer. Therefore the swelling behaviour of microgels in selected solvents as a function of microgel composition is discussed as well. The structured microgels were prepared by first making an aqueous emulsion via the semi-batch emulsion copolymerisation, then dehydrating the system by air drying followed by grinding in a mill. The resulting agglomerates of spherical microgel particles were dispersed in convenient organic solvent media and after that added to the thermosetting solvent-borne acrylic binder system. It was shown that the application of core–shell microgels did not affect the surface appearance and transparency of coatings. Moreover, the presence of microgel network precursors improved corrosion resistance of coatings.     

High temperature mechanical properties of laminated ZrB2–SiC based ceramics

Two laminated ZrB₂-SiC based ceramics were prepared by tape casting and subsequent hot pressing, with BN (LZB) and graphite (LZG ) as interface layers. The LZB specimen presents flexural strength of 381 MPa at room temperature and 111 MPa at 1500 °C; while the LZG specimen shows flexural strength of 414 MPa at room temperature and 377 MPa at 1500 °C. In addition, the flexural strength of LZG specimen is always higher than that of the LZB specimen in the temperature range from room temperature to 1500 °C. Such higher strength is attributed to the healing of surface microcracks and pores by the SiO₂ glass phase, producing less glass phase in graphite interface layers at high temperature.     

Advantages and disadvantages of graphite addition on the characteristics of hot-pressed ZrB2–SiC composites

ZrB₂–SiC–graphite composites with 0–35 vol% graphite flakes were densified via hot-pressing route at the temperature of 1800 °C under the uniaxial pressure of 40 MPa for 1 h. Consolidation, mechanical properties, and microstructure of hot-pressed composites were investigated by variation of graphite content. By the addition of graphite, the relative density of composites increased, and at this hot pressing condition, fully densified composites were fabricated. The highest flexural strength of 366 MPa was measured for composite containing 7.5 vol% graphite, while the maximum Vickers hardness resulted in 2.5 vol% graphite doped one, and its value was equal to 20.8 GPa. Phase analysis of hot-pressed samples revealed the formation of the Zr₃C₂ and B₄C phases besides the main existing ZrB₂, SiC, and graphite phases. The newly carbide phases formed at the surface of ZrB₂ grains. The addition of graphite into the ZrB₂–SiC composites improved the sintering process and caused a fine-grained microstructure.     

Microstructure and properties of ZrB2–SiC composites prepared by spark plasma sintering using TaSi2 as sintering additive

ZrB₂–SiC composites were fabricated by spark plasma sintering (SPS) using TaSi₂ as sintering additive. The volume content of SiC was in a range of 10–30% and that of TaSi₂ was 10–20% in the initial compositions. The composites could be densified at 1600 °C and the core–shell structure with the core being ZrB₂ and the shell containing both Ta and Zr as (Zr,Ta)B₂ appeared in the samples. When the sintering temperature was increased up to 1800 °C, only (Zr,Ta)B₂ and SiC phases could be detected in the samples and the core–shell structure disappeared. Generally, the composites with core–shell structure and fine-grained microstructure showed the higher electrical conductivity and Vickers hardness. The completely solid soluted composites with coarse-grained microstructure had the higher thermal conductivity and Young's modulus.     

Fabrication and properties of ZrB2–SiC–BN machinable ceramics

ZrB₂–SiC–BN ceramics were fabricated by hot-pressing under argon at 1800 °C and 23 MPa pressure. The microstructure, mechanical and oxidation resistance properties of the composite were investigated. The flexural strength and fracture toughness of ZrB₂–SiC–BN (40 vol%ZrB₂–25 vol%SiC–35 vol%BN) composite were 378 MPa and 4.1 MPa m^1/2, respectively. The former increased by 34% and the latter decreased by 15% compared to those of the conventional ZrB₂–SiC (80 vol%ZrB₂–20 vol%SiC). Noticeably, the hardness decreased tremendously by about 67% and the machinability improved noticeably compared to the relative property of the ZrB₂–SiC ceramic. The anisothermal and isothermal oxidation behaviors of ZrB₂–SiC–BN composites from 1100 to 1500 °C in air atmosphere showed that the weight gain of the 80 vol%ZrB₂–20 vol%SiC and 43.1 vol%ZrB₂–26.9 vol%SiC–30 vol%BN composites after oxidation at 1500 °C for 5 h were 0.0714 and 0.0268 g/cm², respectively, which indicates that the addition of the BN enhances oxidation resistance of ZrB₂–SiC composite. The improved oxidation resistance is attributed to the formation of ample liquid borosilicate film below 1300 °C and a compact film of zirconium silicate above 1300 °C. The formed borosilicate and zirconium silicate on the surface of ZrB₂–SiC–BN ceramics act as an effective barriers for further diffusion of oxygen into the fresh interface of ZrB₂–SiC–BN.     

Effect of temperature on the structure and mechanical properties of SiC–TiB2 composite ceramics by solid-phase spark plasma sintering

SiC composite ceramics have good mechanical properties. In this study, the effect of temperature on the microstructure and mechanical properties of SiC–TiB₂ composite ceramics by solid-phase spark plasma sintering (SPS) was investigated. SiC–TiB₂ composite ceramics were prepared by SPS method with graphite powder as sintering additive and kept at 1700 °C, 1750 °C, 1800 °C and 50 MPa for 10min.The experimental results show that the proper TiB₂ addition can obviously increase the mechanical properties of SiC–TiB₂ composite ceramics. Higher sintering temperature results in the aggregation and growth of second-phase TiB₂ grains, which decreases the mechanical properties of SiC–TiB₂ composite ceramics. Good mechanical properties were obtained at 1750 °C, with a density of 97.3%, Vickers hardness of 26.68 GPa, bending strength of 380 MPa and fracture toughness of 5.16 MPa m^1/2.     

Effects of graphite nano-flakes on thermal and microstructural properties of TiB2–SiC composites

In the last decades, the production of ultra-high temperature composites with improved thermo-mechanical properties has attracted much attention. This study focuses on the effect of graphite nano-flakes addition on the microstructure, densification, and thermal characteristics of TiB₂–25 vol% SiC composite. The samples were manufactured through spark plasma sintering process under the sintering conditions of 1800 °C/7 min/40 MPa. Scanning electron microscopy images demonstrated a homogenous dispersion of graphite flakes within the TiB₂–SiC composite causing a betterment in the densification process. The thermal diffusivity of the specimens was gained via the laser flash technique. The addition of graphite nano-flakes as a dopant in TiB₂–SiC did not change the thermal diffusivity. Consequently, the remarkable thermal conductivity of TiB₂–SiC remained intact. It seems that the finer grains and more interfaces obstruct the heat flow in TiB₂–SiC–graphite composites. Adding a small amount of graphite nano-flakes enhances the densification of the mentioned composite by preventing the grain growth.     

Effect of Si content on the microstructure and properties of Ti–Si–C composite coatings prepared by reactive plasma spraying

In this study, Ti–Si–C composite coatings were synthesized via plasma spraying of agglomerated powders prepared by a spray drying/precursor pyrolysis technology using Ti, Si, and sucrose powders. The influence of Si content, ranging from 0 wt% to 24 wt%, on the microstructure, mechanical properties, and oxidation resistance of the composite coatings was investigated. Results show that the phase composition of the Ti–Si–C composite coatings changes with the increasing Si content. The coatings without Si addition consist of TiC and Ti₃O; the coatings with 6–18 wt% Si are composed of TiC, Ti₅Si₃, and Ti₃O; the coatings with Si content of 24 wt% form only TiC and Ti₅Si₃ phases. As the Si content increases, the hardness of the Ti–Si–C composite coatings increases first and then decreases, depending on the intrinsic hardness of the ceramic phases, the brittleness of Ti₅Si₃, and the defects such as pores and cracks. The Ti–Si–C composite coatings have high wear resistance due to the in-situ synthesized high-hardness TiC and Ti₅Si₃. Owing to the high brittleness of Ti₅Si₃, the increasing Si content leads to higher wear volume loss at room temperature, which can be partially improved in high-temperature wear tests. The oxidation resistance of Ti–Si–C composite coatings increases with the increase of Si content, and the higher the oxidation temperature, the more obvious the influence of the Si addition on oxidation resistance.     

Effect of different additives and open porosity on fracture toughness of ZrB2–SiC-based composites prepared by SPS

In this work, Taguchi experimental design technique was applied to determine the most influential additives and SPS parameters for optimizing fracture toughness of ZrB₂–SiC based composites. In this case, nine factors (SiC, C_f, MoSi₂, HfB₂ and ZrC content, milling time of C_f and SPS parameters such as temperature, time and pressure) were examined on four different levels in order to obtain the optimum mixture. A total of 32 mixtures were prepared in accordance to the L32 array proposed by the method. Fracture toughness of all composites was measured by single edge-notch beam test. SEM was applied to evaluate microstructure. It has been concluded that the open porosity up to 10% has no significant effect on fracture toughness but in higher values, it is varied inversely with its changes. The results showed that temperature with 34.7% and SiC with 29.7% have significant effect on fracture toughness. C_f, M.t, HfB₂, pressure and time with 2.3%, 3.2%, 0.05%, 0.44% and 2.3% have influence on fracture toughness, respectively. ZrC has 7.8% and MoSi₂ has 6.3% on fracture toughness.     

In situ studies of oxidation of ZrB2 and ZrB2–SiC composites at high temperatures

High temperature oxidation of ZrB₂ and the effect of SiC on controlling the oxidation of ZrB₂ in ZrB₂–SiC composites were studied in situ, in air, using X-ray diffraction. Oxidation was studied by quantitatively analyzing the crystalline phase changes in the samples, both non-isothermally, as a function of temperature, up to ～1650 °C, as well as isothermally, as a function of time, at ～1300 °C. During the non-isothermal studies, the formation and transformation of intermediate crystalline phases of ZrO₂ were also observed. The change in SiC content, during isothermal oxidation studies of ZrB₂–SiC composites, was similar in the examined temperature range, regardless of sample microstructure and composition. Higher SiC content, however, markedly retarded the oxidation rate of the ZrB₂ phase in the composites. A novel approach to quantify the extent of oxidation by estimating the thickness of the oxidation layer formed during oxidation of ZrB₂ and ZrB₂–SiC composites, based on fractional conversion of ZrB₂ to ZrO₂ in situ, is presented.     

Microstructure and properties of ablative C/ZrC–SiC composites prepared by reactive melt infiltration of zirconium and vapour silicon infiltration

C/ZrC-SiC composites with a density of 3.09 g/cm³ and a porosity of 4.8% were prepared by reactive melt infiltration and vapour silicon infiltration. The flexural strength and modulus were 235 MPa and 18.3 GPa, respectively, and the fracture toughness was 7.0 MPa m^1/2. The formation of SiC and ZrSi₂ during vapour silicon infiltration, at the residual cracks and pores in the C/ZrC, enhanced the interface strength and its mechanical properties. The high flexural strength (223 MPa, c. 95% of the original value) after oxidation at 1600 °C for 10 min indicated the excellent oxidation resistance of the composites after vapour silicon infiltration. The mass loss and linear recession rate of the composites were 0.0071 g/s and 0.0047 mm/s, respectively and a fine ablation morphology was obtained.     

Evaluation of oxy-acetylene flame angle effect on the erosion resistance of SiC/ZrB2–SiC/ZrB2 multilayer coatings fabricated by the shielding shrouded plasma spray technique

In the present study, the effect of oxy-acetylene flame angle on the erosion resistance of SiC/ZrB₂–SiC/ZrB₂ multilayer coatings with the gradient structure was investigated. To this aim, first, the SiC inner layer was applied by the reactive melt infiltration (RMI) technique; then ZrB₂ and ZrB₂–SiC layers with 10, 20 and 30%wt. SiC were applied on graphite by the plasma spraying technique. To prevent the oxidation of ZrB₂ and SiC particles, the plasma spraying process was performed by a solid protective shield. To evaluate the performance of the coatings in erosive environments, the samples were exposed to oxy-acetylene flame at the angles of 30°, 60° and 90° for 360 s; the destruction mechanism of SiC/ZrB₂–SiC/ZrB₂ multilayer coatings appeared to be controlled mechanically and chemically. The results of the erosion test showed that at the low flame angles of about 30°, due to the shear forces of oxy-acetylene flame, mechanical erosion overcame the chemical one. With increasing the flame angle, due to raising the surface temperature, chemical erosion overcame the mechanical one; so, most chemical destruction occurred at the flame angle of 90°. Also, the results of the erosion test showed that the total chemical and mechanical destruction at the angle of 60° was greater than that in other angles. Also, among the coatings tested, SiC/ZrB₂- 20% wt. SiC/ZrB₂ coatings had the best erosion resistance; so, the weight changes under the oxy-acetylene flame at the angles of 30° and 60°, respectively, were about ?0.038%. and ?0.355%; meanwhile, at the angle of 90°, it was about +4.3%.     

Microstructure and mechanical properties of ZrB2–SiC porous ceramic by camphene-based freeze casting

Camphene-based freeze casting technique was adopted to fabricate ZrB₂–SiC porous ceramic with 3-dimensional (3D) pore network. ZrB₂–SiC/camphene slurries (initial solid loading: 20 vol%, 25 vol% and 30 vol%) were prepared for freeze casting. Regardless of initial solid loading, the fabricated sample had dense/porous dual microstructure. The thickness of dense layer was about 200–300 μm. The microstructures of ZrB₂–SiC porous ceramics were significantly influenced by the initial solid loading, which determines the pore size, porosity and mechanical properties of the final products.     

High temperature strength of hot pressed ZrB2–20 vol% SiC ceramics based on ZrB2 starting powders prepared by different carbo/boro-thermal reduction routes

ZrB₂–20 vol% SiC (ZS) ceramics based on ZrB₂ starting powders obtained by different boro/carbo-thermal reductions involving ZrO₂ + B₄C, ZrO₂ + B₄C + C, and ZrO₂ + B, were fully densified by hot pressing at 1900–2000 °C. The flexural strength of these ZS ceramics was measured from room temperature up to 1600 °C. At 1600 °C, the flexural strength of the ceramics is 460 ± 31, 471 ± 32 and 345 ± 11 MPa, respectively. The evolution of the strength as function of temperature is explained in terms of the differences in oxygen content, nature of fracture, grain sizes, grain boundary phases and microstructural defects.     

Hot-pressed ZrB2–SiC composite ceramics: Effect of various Ta-containing additives on the microstructure and mechanical properties

The ZrB₂–SiC composites have been commercially used at ultrahigh temperatures, but it often failed due to their poor toughness. In order to solve this problem, four types of Ta-containing additives (Ta, TaC, TaB₂ and TaSi₂) were used as the “third phase” to regulate the microstructure, so as to enhance the mechanical properties of hot-pressed ZrB₂–20SiC-based ceramics (in vol. %). The incorporation of the additives generated a core–shell structure, which comprised of a ZrB₂ core and a (Zr, Ta)B₂ solid solution shell. The additives helped refine the ZrB₂ grains in addition to the metallic Ta and release the internal stress field generated by the thermal misfit. The interfacial structure was modified by the formation of the coherent core/shell interface and the semi-coherent interface of adjacent ZrB₂ grains and the semi-coherent ZrB₂/(Zr, Ta)C interface in the TaC-additive composite. The addition of TaB₂ or TaC hardened the ZrB₂–20SiC ceramics, whereas the addition of Ta or TaSi₂ reduced the hardness. The fracture toughness was enhanced by the formation of the Ta-containing phases. These phases reduced the stress intensity factor of the crack tip, which was proportional to the intrinsic residual stress. However, the crack-propagation mechanism would be changed by the incorporation of various Ta-containing additives. The decrease in the crack deflection, which was induced by the stronger interfacial bonding force and the significant consumption of SiC, resulted in relatively low toughness in the Ta- and TaC-included samples. The weaker interfacial bonding force in the TaB₂- and TaSi₂-included samples caused an increase in deflection and generated branching, which enhanced the toughness of the TaSi₂-included composites to ～4.72 MPa?m^1/2.