Microstructure-Based Thermochemical Ablation Model of Carbon/Carbon-Fiber Composites.

The microstructure of carbon fiber-reinforced carbon-matrix composites (carbon/carbon composites) has important effects on its ablation performance. However, the traditional macro-ablation methods have underestimated the ablation recession rate and ignored the influence of microstructure. To simulate the ablation of large-sized structures while accounting for the influence of microstructure, it is necessary to modify these methods. In this work, a thermochemical ablation model for carbon/carbon composites is proposed based on the evolution behavior of their microstructure. The ablation recession rate and surface temperature predicted by this model are in good agreement with the experimental results. Through numerical analysis, we found that the ablation recession rate of the material without carbon fibers is much greater than that of the material containing carbon fibers. The ablation recession rate is influenced by the fiber orientation due to the change in thermal conductivity. The anti-ablation efficiency of carbon/carbon composites can be improved by increasing their fiber radius, radiation coefficient, specific heat capacity, interphase density, and thermal conductivity coefficient. The thermochemical ablation model provides a guide for the design of better anti-ablation carbon/carbon composites.

Fabrication of Large Aerogel-Like Carbon/Carbon Composites with Excellent Load-Bearing Capacity and Thermal-Insulating Performance at 1800 °C.

Carbon aerogels (CAs) are attractive candidates for the thermal protection of aerospace vehicles due to their excellent thermostability and thermal insulation. However, the brittleness and low mechanical strength severely limits their practical applications, and no significant breakthroughs in large CAs with a high strength have been made. We report a high-pressure-assisted polymerization method combined with ambient pressure drying to fabricate large, strong, crack-free carbon/carbon (C/C) composites with an excellent load-bearing capacity, thermal stability, and thermal insulation. The composites are comprised of an aerogel-like carbon matrix and a low carbon crystallinity fiber reinforcement, featuring overlapping nanoparticles, macro-mesopores, large particle contact necks, and strong fiber/matrix interfacial bonding. The resulting C/C composites with a medium density of 0.6 g cm-3 have a very high compressive strength (80 MPa), in-plane shear strength (20 MPa), and specific strength (133 MPa g-1 cm3). Moreover, the C/C composites of 7.5-12.0 mm in thickness exposed to an oxyacetylene flame at 1800 °C for 900 s display very low back-side temperatures of 778-685 °C and even better mechanical properties after the heating. This performance makes the composites ideal for the ultrahigh temperature thermal protection of aerospace vehicles where both excellent thermal-insulating and load-bearing capacities are required.

Crack Evolution and Oxidation Failure Mechanism of a SiC-Ceramic Coating Reactively Sintered on Carbon/Carbon Composites.

A SiC ceramic coating was prepared on carbon/carbon composites by pack cementation. The phase composition and microstructure of the coated specimens were characterized using X-ray diffraction instrument and scanning electron microscope. The results showed that the mass-loss percentage of the coated specimen was 9.5% after being oxidized for 20 h. The oxidation failure of the SiC ceramic coating at 1773 K was analysed by non-destructive X-ray computed tomography. The effective self-healing of cracks with widths below 12.7 µm introduced during the coating preparation process and generated while the specimens cooled down from the high oxidation temperature prevented the oxidation of carbon/carbon composites. X-ray computed tomography was used to obtain three-dimensional images revealing internal damage caused by spallation and open holes on the coating. Stress induced by heating and cooling caused the formation, growth and coalescence of cracks, which in turn led to exfoliation of the coating and subsequent failure of oxidation protection.

Epitaxial Grown Carbon Nanotubes Reinforced Pyrocarbon Matrix in C/C Composites with Improved Mechanical Properties.

In order to achieve the highly efficient preparation of high-performance carbon/carbon (C/C) composites, epitaxial grown carbon nanotubes (CNTs) and a pyrocarbon matrix were simultaneously synthesized to fabricate CNT-reinforced C/C composites (CC/C composites). With precise control of the temperature gradient, CNTs and the pyrocarbon matrix could grow synchronously within a 2D needle-punched carbon fiber preform. Surprisingly, the CNTs remained intact within the pyrocarbon matrix at the nano-level, and the CNT-reinforced nano-pyrocarbon matrix was compact, with virtually no gaps and pores, which were tightly connected with the carbon fibers without cracks. Based on the results of Raman analysis, there is less residual stress in the CNT-reinforced pyrocarbon matrix and carbon fibers, and less of a mismatch between the coefficient and thermal expansion. Additionally, CC/C composites fabricated by this method could achieve a low density, open porosity with a large size, and improved mechanical properties. More importantly, our work provides a rational design strategy for the highly efficient preparation and structural design of high-performance CNT-einforced C/C composites.

Tribology and Anti-Ablation Properties of SiC-VN-MoS2/Ta Composite Coatings on Carbon/Carbon Composites from 25 to 800 °C.

To improve the self-lubrication and anti-ablation performances of C/C (carbon/carbon) composites from 25 to 800 °C, we engineered three layers of composite coatings consisting of SiC-VN-MoS2/Ta to deposit on the surface of the C/C composites. The tribology and anti-ablation properties of the composite coatings were experimented under dry sliding wear. The equivalent stress and deformation of the composite coatings are studied. The results show that the CoFs (coefficients of friction) of the C/C composites are decreased by 156% at 800 °C due to the new generated self-lubricating compounds from the MoS2/Ta and VN coating. The anti-ablation of the C/C composites are improved by 25,300% due to the silicon glass, and the generated compounds from V, Mo and Si. The deformation of the C/C substrate under the protection of these coatings looks like a quadrangular star. The cack of the C/C composites is easily generated without the protection from coatings.

rGO based immunosensor amplified using MWCNT and CNF nanocomposite as analytical tool for CA125 detection.

The electrochemical performance of dual layer immunosensor has been studied by employing reduced Graphene oxide (rGO) and its nanocomposites with Carbon Nanofibers (CNFs) and Carbon Nanotubes (CNTs) as supporting matrix for the detection of CA125. The immunosensor determination was based on the formation of antibody - antigen immunocomplex, a decrement in the current response was observed in accordance with the concentration of antigen. Better performance exhibited by rGO/CNF in terms of linearity (99%) and sensitivity 0.65 µA (µg mL-1)-1 can be attributed to its conductivity and surface area. The nanocomposite are employed in the detection of CA125 with linear working range of 10-32 × 10-4 µg mL-1, the limit of detection is found to be 0.28 pg mL-1 rGO nanocomposite with CNT (rGO/CNT) is studied as transducer material. rGO/CNT exhibited better linearity when compared to rGO due to its good conductivity. Thus, graphene nanocomposite transducer materials have vital application in detection of oncomarkers.

Effect of sprayed techniques on the surface microstructure and in vitro behavior of nano-HAp coatings.

Supersonic atmospheric plasma spray (SAPS) technique is a classical method which is employed to coat the carbon/carbon (C/C) composites by nano-hydroxyapatite (HAp) powders to decrease the biologically inert, hydrophobic drawbacks of substrate surfaces. In recent years, profiting from the promoting of energy conservation and environmental protection, more emphasis was placed on industrial manufacturing to simplify the experimental steps. This paper aims to study the preparation of nano-HAp coatings by suspension plasma spray (SPS) instead of the original SAPS technique. A denser, more uniform and less defective coating is successfully fabricated on C/C substrate using SPS technique. More important, fewer surface flaws in SPS coating could be observed by scanning electron microscopy (SEM) which shows that the large drawbacks of the coating have disappeared during spraying process. Meanwhile, except for HAp, phase compositions of the SPS coating appear with slight calcium oxide (CaO, 0.8%) and tricalcium phosphate (TCP, 30.7%), and then all CaO as well as TCP phases transform into dicalcium phosphate anhydrous (DCPA, 60.6%) after microwave-hydrothermal (MH) treatment. Thermal analysis (TG/DSC) reveals that SPS coating (97.51%) has a higher thermal stability than that of the SAPS coating (82.37%). Also, in comparison, the SPS coating after MH treatment (SPS-MH coating) exhibits better thermal properties (92.76%). In addition, compared to the SAPS and SPS coatings, due to the more flaw reduction and phase transformation, SPS-MH coating shows a better biological properties according to the surface microstructure in simulation body fluid (SBF) solution and cell spreading area on coating. The highest corrosion resistance with the current density of 3.9798 × 10-7 A/cm2 and a potential of 0.0419 V is achieved for SPS-MH coating.

Electrical Current Map and Bulk Conductivity of Carbon Fiber-Reinforced Nanocomposites.

A suitably modified resin film infusion (RFI) process was used for manufacturing carbon fiber-reinforced composites (CFRCs) impregnated with a resin containing nanocages of glycidyl polyhedral oligomeric silsesquioxane (GPOSS) for enhancing flame resistance and multi-wall carbon nanotubes (MWCNTs) to contrast the electrical insulating properties of the epoxy resin. The effects of the different numbers (7, 14 and 24) of the plies on the equivalent direct current (DC) and alternating current (AC) electrical conductivity were evaluated. All the manufactured panels manifest very high values in electrical conductivity. Besides, for the first time, CFRC strings were analyzed by tunneling atomic force microscopy (TUNA) technique. The electrical current maps highlight electrically conductive three-dimensional networks incorporated in the resin through the plies of the panels. The highest equivalent bulk conductivity is shown by the seven-ply panel characterized by the parallel (σ//0°) in-plane conductivity of 16.19 kS/m. Electrical tests also evidence that the presence of GPOSS preserves the AC electrical stability of the panels.

Ablation Behavior of the SiC-Coated Three-Dimensional Highly Thermal Conductive Mesophase-Pitch-Based Carbon-Fiber-Reinforced Carbon Matrix Composite under Plasma Flame.

This study is focused on a novel high-thermal-conductive C/C composite used in heat-redistribution thermal protection systems. The 3D mesophase pitch-based carbon fiber (CFMP) preform was prepared using CFMP in the X (Y) direction and polyacrylonitrile carbon fiber (CFPAN) in the Z direction. After the preform was densified by chemical vapor infiltration (CVI) and polymer infiltration and pyrolysis (PIP), the 3D high-thermal-conductive C/C (CMP/C) composite was obtained. The prepared CMP/C composite has higher thermal conduction in the X and Y directions. After an ablation test, the CFPAN becomes needle-shaped, while the CFMP shows a wedge shape. The fiber/matrix and matrix/matrix interfaces are preferentially oxidized and damaged during ablation. After being coated by SiC coating, the thermal conductivity plays a significant role in decreasing the hot-side temperature and protecting the SiC coating from erosion by flame. The SiC-coated CMP/C composite has better ablation resistance than the SiC-coated CPAN/C composite. The mass ablation rate of the sample is 0.19 mg·(cm-2·s-1), and the linear ablation rate is 0.52 µm·s-1.

Reversible Self-Healing Carbon-Based Nanocomposites for Structural Applications.

Reversible Hydrogen Bonds (RHB) have been explored to confer self-healing function to multifunctional nanocomposites. This study has been carried out through a sequence of different steps. Hydrogen bonding moieties, with the intrinsic ability to simultaneously perform the functions of both hydrogen donors and acceptors, have been covalently attached to the walls of carbon nanotubes. The epoxy matrix has been modified to adapt the formulation for hosting self-healing mechanisms. It has been toughened with different percentages of rubber phase covalently linked to the epoxy precursor. The most performant matrix, from the mechanical point of view, has been chosen for the incorporation of MWCNTs. Self-healing performance and electrical conductivities have been studied. The comparison of data related to the properties of nanocomposites containing incorporated functionalized and nonfunctionalized MWCNTs has been performed. The values of the electrical conductivity of the self-healing nanocomposites, containing 2.0% by weight of functionalized multiwalled carbon nanotubes (MWCNTs), range between 6.76 × 10-3 S/m and 3.77 × 10-2 S/m, depending on the nature of the functional group. Curing degrees, glass transition temperatures, and storage moduli of the formulated multifunctional nanocomposites prove their potential for application as functional structural materials.

Tailored N-doped porous carbon nanocomposites through MOF self-assembling for Li/Na ion batteries.

Presently, carbon-based anodes for energy storage, such as graphite for lithium-ion batteries (LlBs) and hard carbon for sodium-ion batteries (SlBs), have low capacity and poor rate properties. However, the capacity and rate capability of these anodes can be improved via morphological control, doping and using nanostructures. In this report, a series of self-assembled N-doped porous carbon nanocomposites (NPCNs) were prepared via pyrolysis of metal-organic frameworks (MOFs)-ZIF-8/carbon nanocomposites grown on various carbon frameworks (1D CNT and/or 2D rGO). It was found that the NPC-CNT@G electrode significantly exhibits superior performance for lithium/sodium storage among the other NPCNs. NPC-CNT@G electrode delivers high initial reversible capacities (986 mAh g-1 at 0.1 A g-1 in LIBs; 315 mAh g-1 at 0.05 A g-1 in SIBs), excellent rate properties (443 mAh g-1 at 5 A g-1 in LIBs; 174 mAh g-1 at 1 A g-1 in SIBs) and durable cycle life (99% capacity retention after 2000 cycles at 5 A g-1 in LIBs, 80% capacity retention after 300 cycle at 1 A g-1 in SIBs). This 'carbon-on-carbon' approach described herein can be applied to make other interesting structures for high performance battery materials.

Quantitative characterization of the carbon/carbon composites components based on video of polarized light microscope.

The components of carbon/carbon (C/C) composites have significant influence on the thermal and mechanical properties, so a quantitative characterization of component is necessary to study the microstructure of C/C composites, and further to improve the macroscopic properties of C/C composites. Considering the extinction crosses of the pyrocarbon matrix have significant moving features, the polarized light microscope (PLM) video is used to characterize C/C composites quantitatively because it contains sufficiently dynamic and structure information. Then the optical flow method is introduced to compute the optical flow field between the adjacent frames, and segment the components of C/C composites from PLM image by image processing. Meanwhile the matrix with different textures is re-segmented by the length difference of motion vectors, and then the component fraction of each component and extinction angle of pyrocarbon matrix are calculated directly. Finally, the C/C composites are successfully characterized from three aspects of carbon fiber, pyrocarbon, and pores by a series of image processing operators based on PLM video, and the errors of component fractions are less than 15%.

In vitro mineralization of MC3T3-E1 osteoblast-like cells on collagen/nano-hydroxyapatite scaffolds coated carbon/carbon composites.

Collagen/nano-hydroxyapatite (collagen/nHA) scaffolds were successfully prepared on carbon/carbon composites as bioactive films using the layer-by-layer coating method. Surface characterizations of collagen/nHA scaffolds were detected by scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. Compressive strengths of the scaffolds were evaluated by a universal test machine. In vitro biological performances were determined using scaffolds seeded with MC3T3-E1 osteoblasts-like cells and cultured in mineralization medium for up to 21 days. In addition, cellular morphologies and several related gene expressions of MC3T3-E1 cells in the scaffolds were also evaluated. Chemical and morphological analysis showed that the scaffolds had uniform pore sizes and unified phase composition. Mechanical testing indicated that the collagen/nHA scaffolds had the highest compressive strength in 50% of strain condition when the proportion of collagen and nano-hydroxyapatite was 1:3. Cellular morphology observations and cytology tests indicated that MC3T3-E1 cells were adhered on these scaffolds and proliferated. SEM photographs and gene expressions showed that mineralized MC3T3-E1 cells and newly formed extra cellular matrix (ECM) filled up the pores of the scaffolds after the 3-week mineralization inducement. Nano-sized apatite particles were secreted from MC3T3-E1 cells and combined with the reconstructed ECM. Collectively, collagen/nHA scaffolds provided C/C composites with a biomimetic surface for cell adhesion, proliferation and mineralized extra cellular matrices formation.

The effect of magnetic field on electrochemically deposited calcium phosphate/collagen coatings.

Nanostructured calcium phosphate/collagen (CaP/COL) coatings were deposited on the carbon/carbon (C/C) composites through electrochemical deposition (ECD) under magnetic field. The effect of magnetic fields with different orientations on the morphology and composition was investigated. Both the morphology and composition of the coatings could be altered by superimposed magnetic field. Under zero magnetic field and magnetic field, three-dimensional network structure consisting of collagen fibers and CaP were formed on the C/C substrate. The applied magnetic field in the electric field helped to form nanostructured and plate-like CaP on collagen fibers. For the ECD under magnetic field, the Ca/P molar ratio of the coatings was lower than the one under B=0. This may be contributed to the decreased electrical resistance or the increased electrical conductivity of electrolyte solutions under magnetic field. The nanosized CaP/COL coatings exhibited the similar morphology to the human bone and could present excellent cell bioactivity and osteoblast functions.