Long-time ablation protection of carbon/carbon composites with different-La2O3-content modified ZrC coating

Long time oxidation protection at ultra-high temperatures or ablation protection has been a choke point for C/C composites. In this study, long time ablation protection of different-La₂O₃-content (5–30 vol.%) modified ZrC coating for SiC-coated carbon/carbon (C/C) composites was investigated. Results showed that ZrC coating with 15 vol.% La₂O₃ had good ablation resistance and could protect C/C composites for at least 700?s at 2160 °C. A high-thermal-stability and low-oxygen-diffusivity oxide scale containing m-ZrO₂ particles and molten phases with La_0.1Zr_0.9O_1.95 and La₂Zr₂O₇ was formed during ablation, offering the ablation protection. La could erode grain boundaries of ZrO₂ to refine ZrO₂ by short-circuit diffusion and m-ZrO₂ particles were retained due to less bulk diffusion than grain-boundary diffusion of La into ZrO₂. The erosion resulted in the formation of molten phases containing fine nano-ZrO₂, which served as viscous binder among m-ZrO₂ particles and crack sealer for the oxide scale.     

ZrC–C and ZrO2–C as Novel Supports of Pd Catalysts for Formic Acid Electrooxidation

The Pd/ZrC–C and Pd/ZrO₂–C catalysts with zirconium compounds ZrC or ZrO₂ and carbon hybrids as novel supports for direct formic acid fuel cell (DFAFC) have been synthesized by microwave‐assisted polyol process. The Pd/ZrC–C and Pd/ZrO₂–C catalysts have been characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), energy dispersive analysis of X‐ray (EDAX), transmission electron microscopy (TEM), and electrochemical measurements. The physical characteristics present that the zirconium compounds ZrC and ZrO₂ may promote the dispersion of Pd nanoparticles. The results of electrochemical tests show that the activity and stability of Pd/ZrC–C and Pd/ZrO₂–C catalysts show higher than that of Pd/C catalyst for formic acid electrooxidation due to anti‐corrosion property of zirconium compounds ZrC, ZrO₂, and metal–support interaction between Pd nanoparticles and ZrC, ZrO₂. The Pd/ZrC–C catalyst displays the best performance among the three catalysts. The peak current density of formic acid electrooxidation on Pd/ZrC–C electrode is nearly 1.63 times of that on Pd/C. The optimal mass ratio of ZrC to XC‐72 carbon is 1:1 in Pd/ZrC–C catalyst with narrower particle size distribution and better dispersion on surface of the mixture support, which exhibits the best activity and stability for formic acid electrooxidation among all the samples.     

Ablation resistance of SiC‐modified ZrC coating prepared by SAPS for SiC‐coated carbon/carbon composites

This study evaluated the ablation resistance of ZrC/SiC coating for carbon/carbon (C/C) composites at different temperatures and heat fluxes, which improved the researches on ultra‐high temperature oxidation of ZrC/SiC system. Results showed that the protection of coating depended on temperature and heat flux. Ablation test for 120 seconds under heat flux of 2.4 MW/m² at 2270°C revealed a good ablation resistance, with the linear ablation rate reduced by 96.4% and the mass gain rate increased by 383.3% compared with those of pure ZrC coating. The good ablation resistance was attributed to the formation of dense oxide scale surface. SiC could improve the compactness of the oxide scale at this temperature by forming SiO₂. A dense scale could not form at 2105°C after ablation for 120 seconds, resulting in a dissatisfactory ablation resistance of the coating. After ablation for 120 seconds at 1738°C, the coating was integrated due to the protection of glassy SiO₂ encapsulated ZrO₂. The coating could not resist the strong shear force from the flame at heat flux of 4.2 MW/m² and was severely damaged after ablation for 60 seconds.     

The preparation of ZrO2–ZrC ceramic microspheres by internal gelation process with sucrose as a carbon source

ZrO₂–ZrC (ZrCO) ceramic microspheres were fabricated by internal gelation and carbothermal reduction. The effect of various carbon sources on the stability of the broth was investigated, the carbon sources which have little effect on the stability of the broth were chosen as the carbon sources for carbothermal reduction, and the component distribution and microstructure of the sintered ZrCO microspheres were analyzed. The results indicate that the broth was stable at room temperature when sucrose was used as the carbon source, and crack-free ZrC–ZrO₂ ceramic microspheres with good sphericity and uniform distribution of ZrC and ZrO₂ could be successfully prepared. Moreover, the ZrC–ZrO₂ ceramic microspheres fabricated have no obvious pores and free carbon.     

Ablation behavior and mechanism of C/C–ZrC–SiC composites under an oxyacetylene torch at 3000 °C

C/C–ZrC–SiC composites with continuous ZrC–SiC ceramic matrix were prepared by a multistep technique of precursor infiltration and pyrolysis process. Ablation properties of the composites were tested under an oxyacetylene flame at 3000 °C for 120 s. The results show that the linear ablation rate of the composites was about an order lower than that of pure C/C and C/C–SiC composites as comparisons, and the mass of the C/C–ZrC–SiC composites increased after ablation. Three concentric ring regions with different coatings appeared on the surface of the ablated C/C–ZrC–SiC composites: (i) brim ablation region covered by a coating with layered structure including SiO₂ outer layer and ZrO₂–SiO₂ inner layer; (ii) transition ablation region, and (iii) center ablation region with molten ZrO₂ coating. Presence of these coatings which acted as an effective oxygen and heat barrier is the reason for the great ablation resistance of the composites.     

Microstructure and mechanical performance evolution of C/C–ZrC composites exposed to oxyacetylene flame

C/C–ZrC composites were prepared by isothermal chemical vapor infiltration (ICVI) combined with reactive melt infiltration (RMI). The ablation behavior of the C/C–ZrC was investigated using an oxyacetylene flame. The effect of ablation time on the microstructure and mechanical property evolution of the composite was studied. The results showed that as the ablation time prolonged, the linear and mass ablation rates of the composite increased firstly and then stabilized. After 15 s ablation, the flexural strength and modulus of the C/C–ZrC were interestingly increased by 141.8% and 40.9%, which reached 138.42 MPa and 6.45 GPa, respectively. During ablation, the preferential oxidation effect of ZrC could mitigate the oxidation of pyrolytic carbon (PyC) and carbon fibers, and the volume change induced by the ZrC →ZrO₂ phase transformation could weaken its bonding with PyC, which was beneficial for releasing the internal residual stresses of the C/C–ZrC and then contributed to the mechanical performance improvement.     

Synthesis of nano-phase ZrC by carbothermal reduction using a ZrO2–carbon nano-composite

Carbothermal reduction of Zr-sucrose gels powders into nano-phase ZrC, or ZrC-Zr(C,O) core-shell powders, via a composite of 2–4 nm sized ZrO₂ and amorphous carbon, is described. Samples with 1.7–20 sucrose-carbon:Zr ratio gels heated to 1495 °C at 10 °Cmin^?1, with 3 and 30 min hold time were studied in detail using; TG, XRD, SEM, TEM, STEM-EDX, and XPS with Ar⁺-ion etching. After 1495 °C, 3 min, the samples with 12-20C:Zr ratios yielded weakly agglomerated 30 to 40 nm sized ZrC particles, surrounded by a dense 5 nm thick shell of Zr(C,O). With 5C:Zr significant amounts of ZrO₂ was present after heating at 1495 °C for 3 min, while after 30 min annealing, ZrC particles without residual amorphous carbon was obtained. Minor amounts of zirconia was found in most samples, which in similarity with the 5 nm Zr(C,O) shell, is believed to stem from post synthesis oxidation.     

Comparing ablation properties of NbC and NbC-25 mol.% ZrC coating on SiC-coated C/C composites

In this work, ablation properties of NbC and NbC-25 mol.% ZrC coating, deposited on SiC-coated C/C composites by supersonic atmospheric plasma spraying, were tested by an oxyacetylene torch. Results showed that, for NbC coating, an unexpected smooth liquid film mostly composed of niobium suboxides (such as NbO₂ and NbO), rather than pure Nb₂O₅, generated during ablation for 45 s. Mechanical erosion resulted from the molten SiO₂, and the relatively low viscosity of the outer oxide layer owing to insufficiently high melting point of niobium suboxides were the key factors for the failure mechanism of NbC coating. While NbC–ZrC coating abated for 90 s has a 97.49 and 66.53% decrease of linear and mass ablation rate relative to NbC coating ablated for 45 s, since ZrO₂ hindering the evaporation of SiO₂ droplets, and more thermal-stable Nb–O–Zr liquid film endow (NbC–ZrC)/SiC/C/C composites with an outstanding anti-ablation property.     

Synthesis of ZrC–SiC Powders by a Preceramic Solution Route

Homogenous liquid precursor for ZrC–SiC was prepared by blending of Zr(OC₄H₉)₄ and Poly[(methylsilylene)acetylene]. This precursor could be cured at 250°C and converted into binary ZrC–SiC composite ceramics upon heat treatment at 1700°C. The pyrolysis mechanism and optimal molar ratio of the precursor were investigated by XRD. The morphology and elements analyses were conducted by SEM and corresponding energy‐dispersive spectrometer. The evolution of carbon during ceramization was studied by Raman spectroscopy. The results showed that the precursor samples heat treated at 900°C consisted of t‐ZrO₂ (main phase) and m‐ZrO₂ (minor phase). The higher temperature induced phase transformation and t‐ZrO₂ converted into m‐ZrO₂. Further heating led to the formation of ZrC and SiC due to the carbothermal reduction, and the ceramic sample changed from compact to porous due to the generation of carbon oxides. With the increasing molar ratios of C/Zr, the residual oxides in 1700°C ceramic samples converted into ZrC and almost pure ZrC–SiC composite ceramics could be obtained in ZS‐3 sample. The Zr, Si, and C elements were well distributed in the obtained ceramics powders and particles with a distribution of 100 ~ 300 nm consisted of well‐crystallized ZrC and SiC phases.     

Laser ablation behaviors of vacuum plasma sprayed ZrC-based coatings

ZrC, ZrC-30 vol% SiC, and ZrC-30 vol% TiC coatings were fabricated by vacuum plasma spray and the laser ablation behaviors were evaluated by a CO₂ laser beam under two heat fluxes (15.9 and 25.5 MW/m²). The phase compositions and microstructures of the coatings after ablation were investigated and the effect of SiC and TiC additives was analyzed. The results showed that the ZrC–SiC coating displayed better ablation resistance compared with the ZrC and ZrC–TiC coatings under 15.9 MW/m² heat flux. While the ZrC–TiC coating exhibited the improved ablation resistance under 25.5 MW/m² heat flux. The continuous and integral ZrO₂–SiO₂ scale provided protective effect for the ZrC–SiC coating. A liquid ZrO₂–TiO₂ layer which owned self-healing ability was formed for the ZrC–TiC coating in both heat fluxes. However, the state of the formed liquid, like amount, viscosity, evaporation, and decomposition, was influenced by the environment and was vital for the ablation resistance. This work might give a clue for designing ultrahigh-temperature ceramics as potential laser ablation–resistant coating materials.     

Ablation behavior of a network interlacing ZrC-VC ceramic coating prepared by a pioneering spillover permeation

A novel network interlacing ZrC-VC ceramic coating was prepared by a pioneering spillover permeation. With the increase of Zr content in the blind vias, the content of ZrC in the coating and the density of the coating all decrease. The density of the coating on C/C–ZrC–SiC substrate is obviously higher than that on C/C substrate. The linear ablation rate of the novel ceramic coated C/C–ZrC–SiC composites was ?0.06 μm/s with about 20 and 1.56 times reduction than C/C composites and C/C–ZrC–SiC composites respectively. The improved ablation resistance was attributed to a dense honeycomb ZrO₂ layer filled with liquid vanadium oxide in the ablation center and the improved thermal radiation.     

Synthesis of a soluble preceramic polymer for ZrC using 2-hydroxybenzyl alcohol as carbon source

A preceramic polymer for ZrC was successfully synthesised by chemical reaction between zirconium oxychloride (ZrOCl₂·8H₂O) and 2-Hydroxybenzyl alcohol via a one-pot route. The molecular structure, thermal properties and pyrolysis behaviour of the precursor were investigated. The results indicated that the precursor might be Zr–O–Zr chain polymer with 2-Hydroxybenzyl alcohol as ligand. The precursor was air-stable and exhibited excellent solubility in common organic solvents. The conversions from precursor to ZrC powders were investigated by TG-DTA, X-ray diffraction, Scanning electron microscope, TEM and Raman spectrum. The precursor underwent a thermal decomposition in four steps, and ZrC powders were formed at 1300°C via carbothermal reduction reaction of ZrO₂ and carbon in argon with ceramic yield of 63.0%. The ZrC particles were fine and exhibited irregular polyhedron morphology with average size in the range of 100–300?nm.     

Synthesis of ZrB2–ZrC hybrid powders via boro-carbothermal reduction of ZrO2 by B4C and carbon black

ZrB₂–ZrC hybrid powders were synthesized by a novel two-step reduction on basis of ZrO₂ + B₄C + C→ ZrC + ZrB₂ + CO reaction in Ar atmosphere, using ZrO₂, B₄C, and carbon black powders as starting materials. Thermodynamics of relevant reactions were evaluated. Effects of excess additions of B₄C and C on phase constituents were investigated. Morphology and chemistry of the powder products were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and transmission electron microscopy (TEM). The results showed that ZrB₂–ZrC hybrid powders with no obvious impurity content could be obtained after heating at 1350 °C for 1 h followed by further reaction at 1700 °C for 1 h with 16 wt% B₄C + 8 wt% C excess addition. Relative contents of the ZrB₂: ZrC phase in the product powders could be conveniently regulated by varying the B₄C and C content in the starting compositions. The resultant powders had good oxidation resistance with an oxidation activation energy value of 433 kJ/mol. Good sinterability of the powder products was demonstrated by hot pressing at 1950 °C for 60min under 30 MPa pressure, which resulted in fully dense ZrB₂–ZrC composite ceramics with Vickers hardness value larger than 18.3 ± 0.6 GPa.     

Microstructure and ablation resistance of ZrCxNy-modified ZrC-SiC composite coating for carbon/carbon composites

Nitrogen-modified ZrC-SiC coatings were prepared by thermal evaporation, in situ reaction, and nitriding process, and the microstructure and ablation property of the coatings were studied. The results showed that nitrogen atoms could replace the carbon atoms and fill the vacancies of ZrC. In addition, the interface of the ZrC phase was optimized. The nitrogen atom solid solution was limited on the coating surface, and the interior of the coating was composed of high-melting point ZrC and SiC ceramics. The ablation test showed a reduction in the ablation rate of the coating after nitriding due to the formation of a dense ZrO₂ layer.     

Synthesis and pyrolysis behavior of a soluble polymer precursor for ultra-fine zirconium carbide powders

A soluble polymer precursor for ultra-fine zirconium carbide (ZrC) was successfully synthesized using phenol and zirconium tetrachloride as carbon and zirconium sources, respectively. The pyrolysis behavior and structural evolution of the precursor were studied by Fourier transform infrared spectra (FTIR), differential scanning calorimetry, and thermal gravimetric analysis (DSC–TG). The microstructure and composition of the pyrolysis products were characterized by X-ray diffraction (XRD), laser Raman spectroscopy, scanning electron microscope (SEM) and element analysis. The results indicate that the obtained precursor for the ultra-fine ZrC could be a Zr–O–C chain polymer with phenol and acetylacetone as ligands. The pyrolysis products of the precursor mainly consist of intimately mixed amorphous carbon and tetragonal ZrO₂ (t-ZrO₂) in the temperature range of 300–1200 °C. When the pyrolysis temperature rises up to 1300 °C, the precursor starts to transform gradually into ZrC, accompanied by the formation of monoclinic ZrO₂ (m-ZrO₂). The carbothermal reduction reaction between ZrO₂ and carbon has been substantially completed at a relatively low temperature (1500 °C). The obtained ultra-fine ZrC powders exhibit as well-distributed near-spherical grains with sizes ranging from 50 to 100 nm. The amount of oxygen in the ZrC powders could be further reduced by increasing the pyrolysis temperature from 1500 to 1600 °C but unfortunately the obvious agglomeration of the ZrC grains will be induced.     

Effects of precursor concentration on the microstructure and properties of ZrC modified C/C composites prepared by precursor infiltration and pyrolysis

To improve the ablation resistance of C/C composites, ZrC modified composites were fabricated by precursor infiltration and pyrolysis combined with gradient chemical vapor infiltration process. The effects of ZrC precursor concentration on the microstructure, mechanical and ablation properties of the composites were studied. Results showed that with the increase of ZrC precursor concentration, the ZrC content and macroscopic uniformity of the composites increased but with obvious ZrC particle aggregation and the flexural strength decreased gradually. As the concentration of ZrC precursor improved to 60%, the fracture mode of the composites transformed from toughness to brittleness which was mainly attributed to the improved graphitization degree and reaction damage of carbon fiber in the precursor pyrolysis process. However, the ablation resistance was enhanced with the increasing precursor concentration which was resulted from the formation of ZrO₂ in center ablation region and continuous ZrO₂ coating in brim region serving as a barrier to heat and oxygen transfer.     

Oxidation and recession of plain weave carbon fiber reinforced ZrB2-SiC-ZrC in oxygen–hydrogen torch environment

The oxidation and recession of four plain weave carbon fiber reinforced ZrB₂-SiC-ZrC composites with different matrix compositions were compared with those of a plain weave carbon fiber reinforced ZrB₂-SiC matrix composite. These composites were fabricated using a silicon melt infiltration method. The composite with the higher ZrC content also formed ZrSi₂ in the matrix instead of residual silicon. The composites were oxidized at 1700 and 1800 °C in an oxygen–hydrogen torch environment. The oxides consisted of ZrO₂ and SiO₂, which formed on the surface of all samples. Carbon fiber at the surface was lost due to oxidation. The recession resistance of ZrB₂-SiC-ZrC matrix composites remained constant at 1700 °C, even if the matrix composition varied, while the resistance at 1800 °C increased with the matrix of ZrC and ZrSi₂. The ZrB₂-SiC-ZrC matrix composite with the higher ZrC and ZrSi₂ compositions formed a sintered ZrO₂-rich layer, which was denser than the ZrO₂-SiO₂ and improved the recession resistance.     

Structure and energetics of ZrC(100)||c-ZrO2(001) interface: A combination of experiments,finite temperature molecular dynamics,periodic DFT and atomistic thermodynamic modeling

The oxidation process of ZrC is very important as it affects its initial excellent mechanical and physical properties. ZrC is an ultra-high temperature ceramic, but forms low refractory oxides at lower temperatures of 500–600 °C. To develop core/shell materials by coating the ZrC surface with another material that forms protective layers on ZrC and prevents it from oxidation (such as SiC), there is the need to study and characterize the oxidized layer surrounding ZrC particles. XPS, ToF-SIMS, TEM-ED and EDX analyses were used to investigate the covering oxidized layer, and polycrystalline ZrO₂(mainly cubic phase) was identified. Some traces of the tetragonal phase are observed to be present as shells around the ZrC particles with a thickness of about 4 nm on the average. Periodic DFT was subsequently used to characterize the interface formed between ZrC(100) and c-ZrO₂(001) phases. A strong interface was noticed mainly with charge transfer from Zr (c-ZrO₂ side) at the interface to O and C (ZrC side) atoms at the interface. The interfacial properties are local to only the first and second layers of ZrO₂, and not on the third and fourth layers of ZrO₂, as Bader charge analysis revealed substantial charge transfer at the interface region with no charge redistribution in the second ZrO₂ layer and subsequent bulk layers. The main physical quantity, ideal work of adhesion (W_ad), used to characterize the interface, remains quite constant for all ZrO₂ layers, and converges at three layers of ZrO₂. The interfacial bonds formed are observed to be stronger than the free surfaces in the corresponding ZrC and c-ZrO₂ used to generate the interface.     

In-situ synthesis of ultra-fine ZrB2–ZrC–SiC nanopowders by sol-gel method

ZrB₂–ZrC–SiC nanopowders with uniform phase distribution were prepared from cost-effective ZrOCl₂·8H₂O by a simple sol-gel method. The synthesis route, ceramization mechanism and morphology evolution of the nanopowders were investigated. ZrB₂–ZrC–SiC ceramic precursor can be successfully obtained through hydrolysis and condensation reactions between the raw materials. Pyrolysis of the precursor was completed at 650 °C, and it produced ZrO₂, SiO₂, B₂O₃ and amorphous carbon with a yield of 39% at 1300 °C. By heat-treated at 1500 °C for 2 h, highly crystallized ZrB₂–ZrC–SiC ceramics with narrow size distribution were obtained. With the holding time of 2 h, both the crystal size and the particle size can be refined. Further prolonging the holding time can lead to serious particles coarsening. Studies on the microstructure evolution of the generated carbon during the ceramic conversion demonstrates the negative effect of the ceramic formation on the structure order improvement of the carbon, due to the large amount of defects generated in it by the boro/carbothermal reduction reactions.     

Ablation behavior of a C/C-ZrC-SiC composite based on high-solid-loading slurry impregnation under oxyacetylene torch

A C/C-ZrC-SiC composite was successfully prepared by high-solid-loading slurry impregnation combined with polymer infiltration and pyrolysis. The microstructure and ablation behavior of the C/C–ZrC–SiC composite were investigated. ZrC particles were uniformly distributed in the matrix, and the obtained C/C–ZrC–SiC composite had a high density of 2.74 g/cm³. After exposure to oxyacetylene flame with a heat flux of 3.86 MW/m² for 120 s, the mass and linear ablation rates of the composite were 0.72 ± 0.11 mg/s and 0.52 ± 0.09 µm/s, respectively. The excellent ablation properties of the composite were attributed to the protection of the matrix by a three-layered oxide scale consisting of ZrO₂/SiO₂-rich/ZrO₂-SiO₂.