Design and preparation of composite coatings with increased reflectivity under high-energy continuous wave laser ablation

High-energy continuous wave (CW) laser ablation can cause severe damage to structural materials in an extremely short time, which generates considerable concern in terms of material safety. For the purpose of reducing or even eliminating such laser-induced damage, a novel composite coating consisting of a boron-modified phenolic formaldehyde resin incorporating ZrC and SiC has been designed and prepared. The experimental results reveal that ZrC and SiC are rapidly oxidized to ZrO₂ and SiO₂ respectively, leading to the formation of a white ceramic layer consisting of ZrO₂ particles and melted SiO₂. After ablation at 1000 W/cm² for 50 s, elemental analysis indicates that no Si can be found in the central ablation zone because of gasification. A relatively compact ZrO₂ layer is formed through the sintering of adjacent ZrO₂ particles, which effectively improves the reflectivity of the coating from 7.3% (before ablation) to 63.5% (after ablation). The high reflectivity greatly reduces the absorption of laser energy. In addition, no obvious ablation defects are observed in the composite coating. The excellent anti-laser ablation performance of the coating makes it a promising system for protecting a material against the effects of long-term CW laser ablation.     

Ablation behavior of C/SiC with YSZ and ZrB2 coatings under high-energy laser irradiation

Carbon fiber-reinforced silicon carbide (C/SiC) composites are important candidates for laser protection materials. In this study, ablation mechanism of C/SiC coated with ZrO₂/Mo and ZrB₂–SiC/ZrO₂/Mo under laser irradiation was studied. ZrB₂–SiC multiphase ceramic and ZrO₂ ceramic were successfully coated on C/SiC composite by atmospheric plasma spraying technology with Mo as transition layer. Phase evolution and morphology of composite were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Moreover, ablation behavior of the composite was investigated by laser confocal microscopy. Results showed that ablation mechanism of C/SiC composite was controlled by phase transformation, thermal reaction, and thermal diffusion, with solid–liquid transition of ZrB₂ and ZrO₂ being dominant factor. Endothermic reaction and good thermal diffusivity of coatings were also important factors affecting ablation performance. Reflectivity effect of ZrO₂ coating was limited under high-energy laser irradiation. Compared with ZrO₂/Mo single-phase-monolayer coating, designed ZrB₂–SiC/ZrO₂/Mo coating showed better ablation performance, and breakdown time of C/SiC increased from 10 to 40 s. The depletion of liquid phase in molten pool was identified as an important factor responsible for rapid failure of C/SiC. The coating failed when the entire liquid phase was consumed within molten pool, followed by rapid damage of C/SiC substrate. Results of this study can provide theoretical guidance and research ideas for design and application of laser protective materials.     

Laser ablation behavior of flake graphite and SiO2 particle-filled hyperbranched polycarbosilane matrix composite coatings

Composite coatings consisting of flake graphite and SiO₂ fillers in a hyperbranched polycarbosilane (HBPCS) matrix were designed and prepared to meet the requirements of laser protection. The laser ablation behavior of the composite coatings were investigated. Control experiments were designed to study the performance of SiO₂ during laser irradiation. The results show that the introduction of SiO₂ changes the anti-laser protective mechanism and can improve the anti-laser property of the coating. High power laser irradiation results in pyrolysis of HBPCS and the formation of SiC particles. Chemical reactions between SiO₂, graphite, and SiC play an important role in consuming energy, and provide an excellent cooling effect to the substrate, leading to decreased temperature. SiC particles formed on the surface of the laser ablation area act as a shield to prevent the laser from irradiating deeper layers of the coating. Due to the cooling effect and thermal stability of SiC, the proposed coating shows a good anti-laser property.     

Microstructure and ablation behavior of SiC coated C/C–SiC–ZrC composites prepared by a hybrid infiltration process

In this study, C/C–SiC–ZrC composites coated with SiC were prepared by precursor infiltration pyrolysis combined with reactive melt infiltration. The pyrolysis behavior of the hybrid precursor was investigated using thermal gravimetric analysis-differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy techniques. The microstructure and ablation behavior of the composites were also investigated. The results indicate that the composites exhibit an interesting structure, wherein a ceramic coating composed of SiC and a small quantity of ZrC covers the exterior of the composites, and the SiC–ZrC hybrid ceramics are partially embedded in the matrix pores and distributed around the carbon fibers as well. The composites exhibit good ablation resistance with a surface temperature of over 2300 °C during ablation. After ablation for 120 s, the mass and linear ablation rates of the composites are 0.0026 g/s and 0.0037 mm/s, respectively. The great ablation resistance of the composites is attributed to the formation of a continuous phase of molten SiO₂ containing SiC and ZrO₂, which seals the pores of the composites during ablation.     

Additively-manufactured multiphase coatings with laser protection ability for the repairing of MoSi2-SiC/SiC coated C/C composites

The Si-SiC-MoSi₂ and Si-SiC coatings were proposed to repair the damaged MoSi₂-SiC/SiC coated C/C composites by laser directed energy deposition. Laser ablation was used to assess the repair effect. Results showed that both the repaired coatings with dense structure could restore the geometric size of damaged area. Compared with the Si-SiC-MoSi₂ coating, the Si-SiC repaired coating with higher laser reflectivity and more free Si could reduce the heat generation and enhance the heat dissipation during ablation, which lowered the maximum temperature by 347.49 K and 810.77 K under 300 W and 500 W ablation for 7 s separately, beneficial to avoid the secondary laser damage of the repaired area.     

Synergistic reinforcement effects of ZrB2 on the ultra-high temperature stability of Cf/SiC composite fabricated by liquid silicon infiltration

A carbon fiber-reinforced silicon carbide (C_f/SiC) composite was fabricated with ZrB₂ via the liquid silicon infiltration (LSI) method. A prepreg was prepared by impregnating the phenolic resin with the ZrB₂ powder. The as-LSIed composites were tested for 5 min with an oxyacetylene torch to evaluate their ablation and oxidation properties under an ultra-high temperature environment. The ZrB₂ powders and SiC matrix between carbon fiber bundles generated a dense ZrO₂-SiO₂ layer, which inhibited further oxygen diffusion into the composite and minimized the ablation and oxidation of the carbon fibers. Weight loss and linear ablation rate were further reduced with the addition of ZrB₂ to the C_f/SiC composite; moreover, the synergistic effect of ZrB₂ and SiC reinforced the ablation properties with increased ZrB₂ content. ZrB₂ also reduced the amount of residual silicon, which was detrimental to the mechanical properties of C_f/SiC composite.     

Enhancement of the microwave absorption properties of PyC-SiCf/SiC composites by electrophoretic deposition of SiC nanowires on SiC fibers

The employment of coating technique on the silicon carbide fibers plays a pivotal role in preparing SiC fiber-reinforced SiC composites (SiC_f/SiC) toward electromagnetic wave absorption applications. In this work, SiC nanowires (SiCNWs) are successfully deposited onto the pyrolytic carbon (PyC) coated SiC fibers by an electrophoretic deposition method, and subsequently densified by chemical vapor infiltration to obtain SiCNWs/PyC-SiC_f/SiC composites. The results reveal that the introduction of SiCNWs could markedly enhance the microwave absorption properties of PyC-SiC_f/SiC composites. Owing to the increasing of SiCNWs loading, the minimum reflection loss of composites raises up to −58.5 dB in the SiCNWs/PyC-SiC_f/SiC composites with an effective absorption bandwidth (reflection loss ≤ −10 dB) of 6.13 GHz. The remarkable enhancement of electromagnetic wave absorption performances is mainly attributed to the improved dielectric loss ability, impedance matching and multiple reflections. This work provides a novel strategy in preparing SiC_f/SiC composites with excellent electromagnetic wave absorption properties.     

A focused review on the tribological behavior of C/SiC composites: Present status and future prospects

Silicon carbide-based ceramic matrix composites have received extensive attention in recent years. Many excellent reviews have reported on the tribological behavior of carbon fiber-reinforced carbon and silicon carbide dual matrix (C/C-SiC) composites. However, a systematic overview of the tribological properties of carbon fiber-reinforced silicon carbide (C/SiC) composites does not exist. This review focuses on C/SiC composites and summarizes the key factors, including internal factors (constituent content, graphitization process, material structure and fiber direction), and various test conditions (pressure and speed, dry and wet, temperature, and counterparts) that affect their tribological behavior. Their wear mechanisms under different conditions are elaborated. Finally, some potential future development directions for improving the performance of C/SiC composites are proposed to provide high-quality ceramic matrix composites for engineering applications. These directions include structural modification, matrix modification, coating technology, laser surface texturing, and material genome method.     

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.     

Research on the ablation mechanism and ablation threshold of CMC-SiCf/SiC by using dual-beam coupling nanosecond laser

Due to the excellent properties of high hardness, oxidation resistance and high temperature resistance, silicon carbide fiber silicon carbide ceramic matrix composite (CMC-SiC_f/SiC) is a typical difficult-to-process material, and is a high-performance advanced material in the aerospace field. In this paper, two groups of ablation experiments (experiment 1 and experiment 2) were performed on CMC-SiC_f/SiC using a dual-beam coupling nanosecond laser, and the ablation morphology was observed by confocal laser microscope. The dual-beam coupling angle of experiment 2 is obtained by experimental method. And through the method of calculation, we get the dual-beam coupling angle of experiment 1 and experiment 2. According to the dual-beam coupling ablation mechanism, based on the theoretical calculation model of non-destructive method D²-lnP₀, combined with the Equivalent Diameter Calculation Method (EDCM) and Equivalent Area Calculation Method (EACM), the laser ablation threshold corresponding to different beam waist size was calculated and compared. The results show that the ablation region of CMC-SiC_f/SiC surface can be divided into three parts: ablation boundary, recast layer area and SiO₂ coverage area. When the pulse energy increases gradually from 300 μJ to 1500 μJ, the variation trend of hole depth is first increase, second decrease, increase again, and finally decrease. The angle between two laser beams affects the waist radius, which in turn affect the laser ablation threshold. The waist of the dual-beam coupling is elliptical, and the orifice of the ablation hole is elliptical. When the waist radius of nanosecond laser is 57 μm, the laser ablation threshold is calculated to be 3.12 J/cm². The main factors affecting the laser ablation threshold are laser pulse repetition frequency (f), beam waist radius (ω₀), laser pulse width (τ), minimum laser power (P_th), and laser wavelength (λ).     

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.     

Ablation resistance and mechanism of SiC–LaB6 and SiC–LaB6–ZrB2 ceramics under plasma flame

In this study, silicon carbide-lanthanum hexaboride (SiC–LaB₆) and silicon carbide–lanthanum hexaboride–zirconium boride (SiC–LaB₆–ZrB₂) ceramics were fabricated by spark plasma sintering at 1900 °C, and their ablation resistance was tested under plasma flames over 2300 °C. The results indicate that the SiC–LaB₆–ZrB₂ ceramic exhibits better ablation resistance than the SiC–LaB₆ ceramic. After ablation under the plasma flame for 60 s, the mass and linear ablation rates of the SiC–LaB₆ ceramic were 15.83 μg/s and 1.08 μm/s, respectively, while those of SiC–LaB₆–ZrB₂ were -8.42 μg/s and -0.27 μm/s. With the addition of ZrB₂, SiC–LaB₆–ZrB₂ ceramic attained a high density and fewer inner oxygen diffusion channels. Moreover, the ZrO₂–La₂O₃–SiO₂ oxide scale with good self-healing ability and excellent stability was formed in the ablation centre, which can retard the further oxidation during ablation.     

Additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic composites

A material extrusion (MEX) technology has been developed for the additive manufacturing of continuous carbon fiber–reinforced silicon carbide ceramic (C_f/SiC) composites. By comparing and analyzing the rheological properties of the slurries with different compositions, a slurry with a high solid loading of 48.1 vol% and high viscosity was proposed. Furthermore, several complex structures of C_f/SiC ceramic composites were printed by this MEX additive manufacturing technique. Phenolic resin impregnation–carbonization process reduces the apparent porosity of the green body and protects the C_f. Finally, the reactive melting infiltration (RMI) process was used to prepare samples with different C_f contents from 0 to 2 K (a bundle of carbon fibers consisting of 1000 fibers). Samples with C_f content of 1 K show the highest bending strength (161.6 ± 10.5 MPa) and fracture toughness (3.72 ± 0.11 MPa·m^1/2) while the thermal conductivity of the samples with the C_f content of 1 K reached 11.0 W/(m·K). This study provides a strategy to prepare C_f/SiC composites via MEX additive manufacturing and RMI.     

The effects of preparation temperature on the SiCf/SiC 3D4d woven composite

Continuous silicon carbide fiber reinforced silicon carbide matrix (SiC_f/SiC) composites have promising applications in aero-engine due to their unique advantages, such as low density, high modulus and strength, outstanding high temperature resistance and oxidation resistance. As SiC fibers are main reinforcements in SiC_f/SiC composites, the crystallization rate and initial damage degree of SiC fibers are seriously influenced by preparation temperatures of SiC_f/SiC composites, namely mechanical properties of SiC fibers and SiC_f/SiC composites are influenced by preparation temperatures. In this paper, KD-II SiC fibers were woven into 3D4d preforms and SiC matrix was fabricated by PIP process at 1100 °C, 1200 °C, 1400 °C and 1600 °C. Digital image correlation (DIC) method was adopted to measure the uniaxial tensile properties of these SiC_f/SiC composites. In addition, finite element method (FEM) based on representative volume element (RVE) was adopted to predict the mechanical properties of SiC_f/SiC composites. The good agreements between numerical results and experimental results of uniaxial tensile tests verified the validity of the RVE. In last, the transverse tensile, transverse shear, uniaxial shear properties were predicted by this method. The predicted results illustrated that axial tensile, transverse tensile and axial shear properties were greatly influenced by the preparation temperatures of SiC_f/SiC composites while transverse shear properties were not significantly various. And the mechanical properties of SiC_f/SiC composites peaked at 1200 °C among these four temperatures while their values reached their lowest points at 1600 °C because of thermal damage and brittle failure of SiC_f/SiC composites.     

Additive manufacturing of high mechanical strength continuous Cf/SiC composites using a 3D extrusion technique and polycarbosilane-coated carbon fibers

A novel additive manufacturing approach is herein reported for manufacturing high mechanical strength continuous carbon fiber-reinforced silicon carbide (C_f/SiC) composite materials. Continuous carbon fibers were coated with polycarbosilane (PCS) using a colloidal evaporative deposition process and then coextruded with high solid content SiC ink. The zeta potential of the SiC ink was adjusted to optimize the printing ability of the suspension. During sintering, small SiC grains and whiskers were generated in the gaps in and around the PCS-coated carbon fibers, which led to the improved flexural strength and density of the composites. Meanwhile, the PCS coating on the surface of the carbon fibers prevented the carbon fibers from reacting with SiO gas generated by reactions between the SiC matrix and SiO₂ and sintering additives (Al₂O₃ and Y₂O₃), effectively preserving the structural integrity of the carbon fibers. Compared to the SiC specimens containing uncoated carbon fibers, the density of the specimens fabricated with coated carbon fibers was increased from 2.51 to 2.85 g/cm³, and the strength was increased from 190 to 232 MPa.     

Enhanced microwave-absorbing properties of FeCo magnetic film-functionalized silicon carbide fibers fabricated by a radio frequency magnetron method

Silicon carbide (SiC) fibers have potential application in microwave absorption materials in recent years. In this study, we provide a new method for improving the microwave-absorbing properties of SiC fibers. Magnetic FeCo films were fabricated on SiC fibers at low temperature and high vacuum by a radio frequency magnetron sputtering method. The properties of FeCo film/SiC fiber (FeCo/SiC_f) composites were investigated. When compared with SiC fiber, the FeCo/SiC_f composites exhibit excellent microwave-absorbing properties in the microwave range, with enhancements in the optimal reflectivity loss from −5.03 to −25.51 dB. This excellent performance may be because of the magnetic loss due to ferromagnetic resonance and interfacial polarization, thus inducing dielectric relaxation. In addition, the magnetic properties of FeCo/SiC_f composites are significantly improved: the value of saturation magnetization reaches up to 41.45 emu/g and the coercivity is 116.27 Oe. In addition, the strength of SiC fiber remains at 99.17% after the fabrication process. The method provided in this study for enhancing the microwave-absorbing properties of FeCo/SiC_f composites will pave a new way for the development of SiC microwave-absorbing materials.     

Spark-plasma sintering of boron carbide–silicon carbide composites at 1400 °C from B4C+Si: Densification and sintering/reaction mechanisms

The feasibility of fabricating novel boron carbide–silicon carbide composites by spark-plasma sintering (SPS) of B₄C+Si powder mixtures at only 1400 °C was investigated. First, it is shown that B₄C can be fully densified at 1400 °C if ~20 vol% Si aids are used, leading to bi-particulate composites constituted by boron carbide (major phase) and SiC (minor phase). The formation of these composites is due to the fact that Si acts as a reactive sintering additive during SPS. Lower and higher proportions of Si aids are not optimal, the former leading to porous bi-particulate composites and the latter to dense triplex-particulate composites with some residual free Si. Importantly, it is also shown that these novel boron carbide–SiC composites are fine-grained, nearly-ultrahard, moderately tough, and more affordable to fabricate, a combination that makes them very appealing for many engineering applications. Second, it is demonstrated that during the heating ramp of the SPS cycles a eutectic melt is formed that promotes full low-temperature densification by transient liquid-phase sintering if sufficient Si aids are used. Otherwise, a subsequent stage of solid-state sintering is required at higher temperatures once the eutectic liquid has been consumed in the in-situ formation of SiC. And third, it is demonstrated that during SPS the original B₄C undergoes a gradual isostructural crystallographic transition towards a Si-doped carbon-deficient boron carbide that is more relevant with increasing proportion of Si aids, and it is identified that the carbon source for the formation of SiC is almost exclusively the carbon exsoluted from the B₄C crystals themselves during their isostructural transition. Finally, implications of interest for the ceramic and hard-material communities are discussed.     

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.     

Strengthening/toughening of 2D C/SiC composites by coating

SiC and SiC_w/SiC coatings were prepared on two-dimensional carbon fiber reinforced silicon carbide ceramic matrix composites (2D C/SiC), and strengthening/toughening of the composite by the coatings was investigated. After coating, the density of the C/SiC composites was increased effectively and the mechanical properties were improved significantly. Compared with SiC coating, SiC_w/SiC coating showed the more significant effect on strength/toughness of the composites. Coatings had two effects: surface strengthening and matrix strengthening. The latter was the dominant effect. The surface strengthening can increase the crack initiation stress, while the matrix strengthening can enhance the crack propagation resistance. The former effect increased the strength and the latter effect increased the toughness.     

Microstructural evolution during the infiltration of boron carbide with molten silicon

The previously reported model that accounts for the formation of the core-rim structure in reaction-bonded boron carbide composites (RBBC) is expanded and validated by additional experimental observations and by a thermodynamic analysis of the ternary B–C–Si system. The microstructure of the RBBC composites consists of boron carbide particles with a core-rim structure, β-SiC and some residual silicon. The SiC carbide particles have a polygonal shape in composites fabricated in the presence of free carbon, in contrast to the plate-like morphology when the initial boron carbide is the sole source of carbon. In the course of the infiltration process, the original B₄C particles dissolve partly or fully in molten silicon, and a local equilibrium is established between boron carbide, molten silicon and SiC. Overall equilibrium in the system is achieved as a result of the precipitation of the ternary boron carbide phase B₁₂(B,C,Si)₃ at the surface of the original boron carbide particles and leads to the formation of the rim regions. This feature is well accounted for by the “stoichiometric saturation” approach, which takes into account the congruent dissolution of B₄C particles. The SiC phase, which precipitates form the silicon melt adopts the β-allotropic structure and grows preferably as single plate-like particles with an {1 1 1}_β habit plane. The morphology of the SiC particles is determined by the amount of carbon available for their formation.