Vapor Infiltration Research Articles

Measurement of Residual Stress in Silicon Carbide Fibers of Tubular Composites Using Raman Spectroscopy

Silicon carbide (SiC) fiber-reinforced ceramic matrix (SiCf/SiCm) composites have been identified as potential materials for nuclear fuel cladding. These composites are fabricated by braiding the SiC fibers around a mandrel into a cylindrical tube and then densifying this preform with SiC matrix using chemical vapor infiltration (CVI). However, during this fabrication process residual stresses develop in the composite, either due to the mechanical braiding process or due to high temperature CVI deposition of the SiC matrix phase. Micro-Raman spectroscopy has been employed to measure the residual stress in the SiC fibers at various stages of the fabrication process. Samples of the composite were analyzed after mechanical braiding and at 33%, 66% and 100% CVI densification of the composites. Raman spectra obtained at the above stages revealed significant band shifts of the SiC peaks and these peak-shift corresponded to -716 MPa of residual stress following the braiding process and -1075 MPa after the densification process. Interestingly, the Raman spectra also revealed carbon bands whose origin was traced to the presence of nanoscale turbostratic graphite throughout the nanograined SiC microstructure.

Preparation and characterization of carbon felt/carbon composites by chemical vapor infiltration process

Preparation and characterization of carbon felt/carbon composites by chemical vapor infiltration process

Enhanced mechanical property and tunable dielectric property of SiCf/SiC-SiBCN composites by CVI combined with PIP

The SiBCN matrix via chemical vapor infiltration (CVI) or/and polymer infiltration pyrolysis (PIP) technologies was orderly introduced to SiCf/SiC composites to optimize the mechanical property and electromagnetic (EM) shielding effectiveness simultaneously. The BN interface with the thickness of 350 nm was designed to obtain a little stronger interface bonding. The flexural strength of SiCf/SiC-SiBCN composites reached 545.45±29.59 MPa thanks to the crack deflection between the CVI SiC and CVI SiBCN, as well as CVI SiBCN and PIP SiBCN matrix because of the modulus difference between them. The fracture toughness (KIC) with the value of 16.02±0.94 MPa·m1/2 was obtained owing to the extension of crack propagation path. The adverse effect of stronger interface bonding was eliminated by the design of matrix microstructure for SiCf/SiC-SiBCN composites. The thermal conductivity in the thickness direction was 7.64 W·(m·K)−1 at 1200 °C and the electric resistivity decreased to 1.53×103 Ω·m. The tunable dielectric property was obtained with the coordination of wave-absorption CVI SiBCN matrix and impedance matching PIP SiBCN matrix, and the total shielding effectiveness (SET) attained 30.01 dB. It indicates that the SiCf/SiC-SiBCN composites have great potential to be applied as structural and functional materials.

Influence of crystallinity on the corrosion rate of chemically vapor‐infiltrated SiCf/SiC composites under 310°C hydrothermal condition

AbstractThe rationale of this work was to investigate the effect of crystallinity on corrosion rate of chemically vapor‐infiltrated (CVI) SiCf/SiC composites. SiCf/SiC composites were fabricated from fabric preform with densifying by CVI. To evaluate the effect of crystallinity on the behavior of SiCf/SiC composite, the infiltration temperature was increased from 1000 to 1100°C with 25°C intervals. X‐ray diffraction and Raman spectroscopy results indicated the diffraction peaks, as the infiltration temperature elevated, become sharp and the transverse optical (TO) and longitudinal optical (LO) phonon peak of the composite increased, respectively. Hydrothermal corrosion tests were performed on the polished surface in a static autoclave at a DI water for 7 and 30 days to evaluate the relation of crystallinity and the microstructure of the composite. Low infiltration temperature revealed columnar growth structure at the matrix after corrosion while weight loss behavior had a linear decreasing tendency from 1000 to 1075°C. These findings are particularly important for determining the infiltration temperature which changes the crystallinity of the SiC phase, and hence the corrosion rate of SiCf/SiC composites.

Mechanical property and toughening mechanism of 2.5D C/C-SiC composites with high textured pyrocarbon interface

The application of C/C-SiC composites remains a challenge because of the poor mechanical properties induced by the liquid silicon infiltration method. In this study, a thick high textured pyrolytic carbon (HT PyC) interface manufactured by chemical vapor infiltration (CVI) was used to protect the carbon fibers and improve the flexural properties. The microstructure of HT PyC, its flexural properties, and its associated strengthening and toughening mechanisms were analyzed on the C/C-SiC composites. The results showed that the bending strength of the C/C-SiC composites was 344.74 MPa, which is nearly 31.82% higher than that of C/C composites. The fracture mode transformed from brittle fracture to pseudoplastic fracture owing to the addition of SiC, and the C/C-SiC composites maintained a better toughness compared to C/C composites. Multiple mechanisms of strength and toughness improvement were found to be responsible for the excellent performance of the C/C-SiC composites. The HT PyC interface played a critical role in the excellent flexural properties. The strong bonding among the carbon layers and high interfacial strength between the fiber and HT PyC led to the increase of strength. Besides, the improvement in toughness was attributed to the multiple effects of the carbon-layers deformation, cracks deflection and propagation caused by the bridging areas, sublayers, nano- and micro-scale cracks.

Synthesis and characterisation of Cf/SiC composites with modified silicon carbide matrix

Cf/SiC composites with multilayer [(PyC/SiC)n; n = 4] interface and modified silicon carbide matrix were prepared through isothermal isobaric chemical vapor infiltration (ICVI) technique and characterised room temperature mechanical properties. The monotonic tensile properties were studied at elevated temperature (i.e. 1250 °C, and 1350 °C) and compared with room temperature tensile properties. The tensile strength at RT, 1250 °C, and 1350 °C of the composite was found to be 193 ± 10 MPa, 238 ± 14 MPa, and 189 ± 20 MPa respectively. This paper also focusses the effect of thermal exposure of composites on residual tensile strength. The enhanced strength and toughness behaviour observed for the prepared composites because of the presence of multi-layer interface and modified matrix (SiC/Si-B-C/SiC). SEM microstructural studies carried out on tested specimens and cross section of prepared composites revealed the evidence for the self-healing behaviour from the modified matrix.

Effect of SiCnws on flexural strength of SiCf/HfC-SiC composites after impact and ablation

SiC nanowires (SiCnws) modified SiCf/HfC-SiC composites were prepared by precursor infiltration and pyrolysis (PIP) and chemical vapor infiltration (CVI) methods. The microstructure, flexural strengths, impact and impact-ablation tests of the composites with and without SiCnws were investigated. The results showed that after introducing SiCnws, not only the retention rate of HfC ceramic produced by PIP was increased obviously, but also the fracture displacement of the modified composites was reduced due to the enhancement effect of SiCnws at interface between SiC fiber and matrix. After impact and impact-ablation, the strength retention of SiCnws modified composites was 91.6 % and 69.1 % respectively, higher than that of the composites without SiCnws (85.2 % and 54.8 %). As the impact resistance of the modified composites was improved by the pull-out and bridging of SiCnws, the ablation resistance of the impacted composites was enhanced as well.

Effects of CVI SiC amount and deposition rates on properties of SiCf/SiC composites fabricated by hybrid chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) routes

The SiCf/SiC composites have been manufactured by a hybrid route combining chemical vapor infiltration (CVI) and precursor infiltration and pyrolysis (PIP) techniques. A relatively low deposition rate of CVI SiC matrix is favored ascribing to that its rapid deposition tends to cause a ‘surface sealing’ effect, which generates plenty of closed pores and severely damages the microstructural homogeneity of final composites. For a given fiber preform, there exists an optimized value of CVI SiC matrix to be introduced, at which the flexural strength of resultant composites reaches a peak value, which is almost twice of that for composites manufactured from the single PIP or CVI route. Further, this optimized CVI SiC amount is unveiled to be determined by a critical thickness t0, which relates to the average fiber distance in fiber preforms. While the deposited SiC thickness on fibers exceeds t0, closed pores will be generated, hence damaging the microstructural homogeneity of final composites. By applying an optimized CVI SiC deposition rate and amount, the prepared SiCf/SiC composites exhibit increased densities, reduced porosity, superior mechanical properties, increased microstructural homogeneity and thus reduced mechanical property deviations, suggesting a hybrid CVI and PIP route is a promising technique to manufacture SiCf/SiC composites for industrial applications.

Retained strength of UHTCMCs after oxidation at 2278 K

In the frame of Horizon 2020 European C3HARME research project, the manufacture of ZrB2-based CMCs was developed through different processes: slurry infiltration and sintering, radio frequency chemical vapour infiltration (RF-CVI) and reactive metal infiltration (RMI). To assess the high temperature stability, room temperature bending strength was measured after oxidizing the samples at 2278 K and compared to the strength of the as-produced materials. Microstructures were analysed before and after the thermal treatment to assess the damage induced by the high temperature oxidation. Short fibre-reinforced composites showed the highest retained strength (>80%) and an unchanged stress–strain curve.

Fabrication of SiCf/SiC composites through hybrid processing via chemical vapor infiltration, electrophoretic deposition, and liquid silicon infiltration

ABSTRACT The present work demonstrates the effectiveness of a novel hybrid process comprising chemical vapor infiltration (CVI), electrophoretic deposition (EPD), and liquid silicon infiltration (LSI) techniques for the successful fabrication of low-porosity SiCf/SiC composites. For this purpose, fiber/matrix interphase dual coating layers of BN and SiC were coated onto SiC fabrics using CVI. A ceramic matrix consisting of SiC and carbon black nanoparticles was then infiltrated into the fine voids of the fabrics using EPD. Finally, LSI was performed to obtain dense microstructures with low porosities by filling the remaining small gaps and reacting Si with C to form SiC. Microstructural results observed by scanning electron microscopy revealed a dense structure with no damage to the fibers. The experimental density was found to be 2.62 g/cc, with an open porosity of 0.55. The room-temperature flexural strength was evaluated to be 111 MPa, and the composites displayed little fiber pull-out.

Ablation and heat insulation performances of nose-shaped ZrC-C composites with gradient pore structure

Nose-shaped ZrC-C composites with gradient pore structure (ZrC-CGS) were successfully prepared by isothermal chemical vapor infiltration using ZrC skeleton as preform. Pyrolytic carbon with medium texture was deposited around ZrC skeleton. From the top to back, the porosity of the ZrC-CGS composites increased gradually from 0% to 62.9%. Compared with the ZrC-C composites with dense structure (ZrC-CDS), the mass ablation rate of the ZrC-CGS composites decreased by 15.3% and the heat resistance capacity increased by 45.6%, and their coefficients of thermal expansion decreased obviously in the temperature range of 200–1500 °C. The simulation results showed that the residual thermal stress and back temperature of the ZrC-CGS composites are lower than those of the ZrC-CDS composites. This work provides an effective strategy for designing and preparing ultra-high temperature composites having both ablation and heat insulation performances by controlling the pore structure and distribution.

Synthesis, structure, and properties of carbon/carbon composites artificial rib for chest wall reconstruction

In this work, braided carbon fiber reinforced carbon matrix composites (3D-C/C composites) are prepared by chemical vapor infiltration process. Their composite structure, mechanical properties, biocompatibility, and in vivo experiments are investigated and compared with those of traditional 2.5D-C/C composites and titanium alloys TC4. The results show that 3D-C/C composites are composed of reinforced braided carbon fiber bundles and pyrolytic carbon matrix and provide 51% open pores with a size larger than 100 μm for tissue adhesion and growth. The Young’s modulus of 3D-C/C composites is about 5 GPa, much smaller than those of 2.5D-C/C composites and TC4, while close to the autogenous bone. 3D-C/C composites have a higher tensile strength (167 MPa) and larger elongation (5.0%) than 2.5D-C/C composites (81 MPa and 0.7%), and do not show obvious degradation after 1 × 106 cyclic tensile loading. The 3D-C/C composites display good biocompatibility and have almost no artifacts on CT imaging. The in vivo experiment reveals that 3D-C/C composites artificial ribs implanted in dogs do not show displacement or fracture in 1 year, and there are no obvious proliferation and inflammation in the soft tissues around 3D-C/C composites implant. Our findings demonstrate that 3D-C/C composites are suitable for chest wall reconstruction and present great potentials in artificial bones.

High-temperature oxidation behavior of C/C composites in wet oxygen: Experiment and first-principle calculations

The oxidation behaviors of carbon/carbon composites prepared by chemical vapor infiltration method in wet oxygen were investigated by experiments and first-principle calculations. The results showed that the graphite components in mixed structure were easily destroyed and transformed into amorphous carbon in wet oxygen, accelerating the weight loss of C/C composites. The reason was ascribed to that hydroxyl radicals promoted the surface and inward diffusion of O atoms by uneven distribution of charges and formation of an exothermic reaction. Besides, the H transfer as a feasible way could result in the gather of epoxy radicals, increasing the risk of cracking.

Safety assessment of the film boiling chemical vapor infiltration (FB-CVI) process through a system-theoretic accident model and process (STAMP)

Film boiling chemical vapor infiltration (FB-CVI) is considered as one of the fastest process methodologies for manufacturing carbon-carbon (C–C) composite products and possesses various advantages compared to conventional methodologies. However, there are safety concerns associated with this process for large-scale manufacturing, mainly owing to the intrinsic nature of the precursor and the process conditions. Considering the multifunctional interactions of the various systems during the process, a system-theoretic process analysis (STPA)/system theoretic accident model and process (STAMP) model is used to perform a safety analysis of the hazardous states of the FB-CVI process at the system level. As a case study, the FB-CVI process equipment employed for the manufacturing of C–C composites is considered. The safety constraints present in the system are assessed for adequacy through a hazard analysis by STPA/STAMP. The analysis through STPA/STAMP demonstrated the capability to create proactive strategies for the design and realization of process equipment that can be employed to manufacture C–C composite products through the FB-CVI process.

Effect of methane and acetaldehyde precursor on the microstructures of pyrocarbon films grown on quartz substrates

The microstructure of pyrolytic carbon significantly affects the performance of aircraft brake discs. In this study, to explore the effect of precursor on the microstructure of pyrocarbon, two types of pyrocarbon films were grown on the quartz glass substrates by isothermal isobaric chemical vapor infiltration using methane and acetaldehyde as precursors. The microstructures of both the films and their formation mechanisms were investigated and compared. The thicknesses of the pyrocarbon films from methane and acetaldehyde were approximately 860 nm and 986 nm, respectively. The film from acetaldehyde comprised quite a few carbon nanoflakes with sizes in the range of 100–200 nm. However, the film from methane exhibited lots of small and dense carbon layers, with a large number of carbon particles of about 20 nm size. Compared to the methane deposited film, the lattice fringes of the carbon layers in the acetaldehyde deposited film were more ordered and had a better orientation. Moreover, the acetaldehyde deposited film had fewer defects owing to the higher sp2/sp3 ratio than that of the methane deposited film. This study may provide new insights into the selection of precursors for preparing pyrocarbon.

Effects of fabrication processes on the properties of SiC/SiC composites

Precursor infiltration and pyrolysis (PIP) and chemical vapor infiltration (CVI) were used to fabricate SiC/SiC composites on a four-step 3D SiC fibre preform deposited with a pyrolytic carbon interface. The effects of fabrication processes on the microstructure and mechanical properties of the SiC/SiC composites were studied. Results showed the presence of irregular cracks in the matrix of the SiC/SiC composites prepared through PIP, and the crystal structure was amorphous. The room temperature flexural strength and modulus were 873.62 MPa and 98.16 GPa, respectively. The matrix of the SiC/SiC composites prepared through CVI was tightly bonded without cracks, the crystal structure had high crystallinity, and the room temperature bending strength and modulus were 790.79 MPa and 150.32 GPa, respectively. After heat treatment at 1300 °C for 50 h, the flexural strength and modulus retention rate of the SiC/SiC composites prepared through PIP were 50.01% and 61.87%, and those of the composites prepared through CVI were 99.24% and 96.18%, respectively. The mechanism of the evolution of the mechanical properties after heat treatment was examined, and the analysis revealed that it was caused by the different fabrication processes of the SiC matrix. After heat treatment, the SiC crystallites prepared through PIP greatly increased, and the SiOxCy in the matrix decomposed to produce volatile gases SiO and/or CO, ultimately leading to an increase in the number of cracks and porosity in the material and a decrease in the material load-bearing capacity. However, the size of the SiC crystallites prepared through CVI hardly changed, the SiC matrix was tightly bonded without cracks, and the load-bearing capacity only slightly changed.

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.

Development of C/SiC Fasteners for High-Temperature Applications

Continuous carbon fiber reinforced silicon carbide (C/SiC) ceramic matrix composites are the candidate materials for high-temperature structural applications owing to their high specific strength, low coefficient of thermal expansion, and moderate thermal conductivity. C/SiC based fasteners provide reliability with oxidation resistance up to 1,650°C for joining such C/SiC structural components used in reusable launch vehicles for space applications. The present study describes the methodology to realize C/SiC based M8 fasteners by isothermal-isobaric chemical vapor infiltration process using 2D-stitched carbon fabric preforms. The realized fasteners exhibited a density of 2.10 g/cm3, a tensile strength of 191 ± 3 MPa, a shear strength of 230 ± 69 MPa in non-threaded and 150 ± 86 MPa in threaded regions of shank at room temperature, a high-temperature tensile strength of 170 ± 12 MPa, and a tensile modulus of 70 ± 8 GPa at 1,100°C in the atmospheric conditions. The tensile failure of the C/SiC bolts was observed to depend upon the relative dimensions of fillet radius and thread root radius, wherein a small fillet radius was observed to be detrimental, as it resulted in failure at the head-shank interface of the bolts. The scanning electron microscope images of tensile tested C/SiC bolts indicate extensive fiber pullout, characteristic of quasi-ductile failure of bolts. It is clearly evident from the studies that the C/SiC fasteners are a promising alternative over the currently used molybdenum alloy fasteners.

Embedded sensors in additively manufactured silicon carbide

Silicon carbide (SiC) components are being considered for a wide range of nuclear applications due to their high-temperature strength retention, low neutron absorption, chemical inertness, and dimensional stability under neutron irradiation. However, machining and joining of SiC components have traditionally limited its application to relatively simple geometries. Recent work has demonstrated additive manufacturing of complex, high-purity, crystalline SiC components using a combination of binder jet printing and densification via chemical vapor infiltration (CVI). The process lends itself to embedding of fuel, absorbers, moderators, and sensors at strategic locations within a component. The latter could allow for enhanced in situ performance monitoring of limiting fuel temperatures, self-shielded neutron flux, and potentially spatially distributed strain within complex SiC components if sensors can be successfully embedded during CVI. This work describes (1) methods for embedding sensors; (2) thermodynamic analyses and material compatibility testing for identifying sensors capable of surviving high temperatures and exposure to hydrogen and hydrogen chloride during CVI; and (3) nuclear applications for embedded sensors, including potential failure modes during fabrication and during reactor operation. Molybdenum-sheathed thermocouples were successfully embedded in a complex SiC component, whereas niobium-sheathed high-temperature irradiation-resistant thermocouples started to drift as soon as the reactant gases were introduced and ultimately failed during CVI due to severe constrained expansion, potentially resulting from niobium hydride formation in the low-temperature region of the CVI system. Optical fibers were successfully embedded in SiC, but further work is needed to protect the fragile fiber leads after their protective coatings are removed during CVI.

Preparation and mechanical characteristics of fine‐woven cloth and punctured felt preform Cf/C‐SiC‐ZrC composite

AbstractA 3D architecture carbon fiber preform, specifically fine‐woven cloth and punctured felt preform, is used to manufacture a novel advanced Cf/C‐SiC‐ZrC composite. The composite matrix is produced by chemical vapor infiltration (CVI) plus precursor infiltration and pyrolysis (PIP) process and finalized by using a chemical vapor deposition (CVD) of SiC coating to make the final density of the material reach 1.95 g/cm3. The organic precursors of SiC and ZrC have a weight ratio of 4:1 in a xylene solute. The composite mechanical properties, such as tensile, compression, bending, shear, and Z‐direction load bearing, are introduced under analysis to find possible applications for the composite. What is more, scanning electron microscope (SEM) images are employed to illustrate the failure behavior of the ceramic composite. The results showed that the punctured filament tows will be beneficial, not only for the composite to withstand compression force up to 308.6 MPa and shear strength to 18.14 MPa but also for the alternatively stacked weave piles and short fiber layers to support the punctured bundles, as well as to hold the composite structure under mechanical forces from different orientations, which is believed to reinforce the ceramic matrix for some high pressure and severe ablation applications.