Pyrolytic Carbon Layer Research Articles

Influence of Carbon Content on Element Diffusion in Silicon Carbide-Based TRISO Composite Fuel

The coating layers of Tri-structural Isotropic Particles (TRISO) serve to protect the kernel and act as barriers to fission products. Sintering aids in the silicon carbide matrix variably react with TRISO coating layers, leading to the destruction of the coating layers. Investigating how carbon content affects element diffusion in silicon carbide-based TRISO composite fuel is of great significance for predicting reactor safety. In this study, silicon carbide-based TRISO composite fuels with different carbon contents were prepared by adding varying amounts of phenolic resin to the silicon carbide matrix. X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) were employed to characterize the phase composition, morphology, and microstructure of the composite fuels. The elemental content in each coating layer of TRISO was quantified using Energy-Dispersive X-ray Spectroscopy (EDS). The results demonstrated that the addition of phenolic resin promoted the uniform distribution of sintering aids in the silicon carbide matrix. The atomic percentage (at.%) of aluminum (Al) in the pyrolytic carbon layer of the TRISO particles reached its lowest value of 0.55% when the phenolic resin addition was 1%. This is because the addition of phenolic resin caused the Al and silicon (Si) in the matrix to preferentially react with the carbon in the phenolic resin to form a metastable liquid phase, rather than preferentially consuming the pyrolytic carbon in the outer coating layer of the TRISO particles. The findings suggest that carbon addition through phenolic resin incorporation can effectively mitigate the deleterious reactions between the TRISO coating layers and sintering aids, thereby enhancing the durability and safety of silicon carbide-based TRISO composite fuels.

Analysis of micro-defect-induced cracking in the IPyC layer of TRISO particle with the XFEM

PurposeWe use the extended finite element method (XFEM) to model the whole process of initiation and propagation of cracks in the inner dense pyrolytic carbon (IPyC) layer of tri-structural isotropic (TRISO) particle induced by the microdefect in an irradiation-induced thermomechanical coupling environment and study the effect of microdefect sizes on the propagation path.Design/methodology/approachThe irradiation-induced thermal–mechanical coupling analysis is first conducted for the representative volume element (RVE) of the TRISO particle by using the conventional finite element method (CFEM) so that the stress distribution is obtained. The stress results are then restored for the enriched elements, and the simulation of crack initiation and propagation is eventually carried out by using the XFEM.Findings1. As a crack initiates in the IPyC layer, it will terminate at the free edge of the RVE TRISO particle in the end. 2. The size of the microdefect has a significant impact on the propagation path.Originality/valueThe ceramic dispersion microencapsulated (CDM) fuel is a good accident-resistant fuel whose safe operation is crucial to the safety and reliability of the whole nuclear reactor. It is of great scientific significance and practical value to study the irradiation-induced thermomechanical coupling stress distribution and cracking behavior in the IPyC layer of TRISO particles for the CDM fuel. Crack initiation and propagation analysis is challengeable for this complex multi-layer structure. This can help understand the failure mechanism of TRISO particles and evaluate the operation safety of the reactor.

Fracture mechanics approach to TRISO fuel particle failure analysis

Weibull stress-based methods for failure probability assessment have been developed and analyzed to assess the integrity of tristructural isotropic (TRISO) fuel particles during fuel life cycles and accident operating conditions. While simple, these methods entail a number of drawbacks when stress concentrates near crack tips, including finite element mesh size dependency when the Weibull stress is averaged over the finite element domain. Fracture mechanics approaches involving the use of interaction integrals eliminate this lack of mesh convergence and produce consistent fracture predictions. In this work, we use an interaction integral approach to computing stress intensity factors for a crack in the inner pyrolytic carbon layer perpendicular to the silicon carbide layer, which is simplified representation of a failure mode in TRISO particles. The interface between these two TRISO layers has been shown to become porous, which we simulate by considering a transition of mechanical properties over such porous length, i.e. the layers are modeled as a functionally graded material. Aspects such as porosity and thermal and irradiation eigenstrains are considered in computing the stress intensity factor from a fracture mechanics approach and compared with the known Weibull stress failure approach. The methodology introduced in this paper enables a more general fracture probability assessment in TRISO particles and eliminates the need to identify best suited parameters when using local or averaged stress-based failure criterion. Finally, the numerical sensitivity studies show how parameters such as the porous transition zone length, the material stiffness, and creep affect the probability of TRISO fuel particle failure.

Toward understanding the damage behavior during orthogonal cutting of 2.5D C/SiC composite based on multi-scale modeling and high-speed photography

2.5D C/SiC composite has been a critical high temperature material for aerospace filed due to its excellent wear, high temperature and oxidation resistance. Understanding the cutting damage behavior is crucial for achieving the high reliability application. This paper presents an in-depth study on damage behavior and material removal mechanism during orthogonal cutting of 2.5D C/SiC composite based on multi-scale modeling and high-speed photography. A three-dimensional numerical micro-macro multi-scale model is established considering the characteristics of the brittle SiC matrix, the isotropic carbon fiber reinforcement, and the pyrolytic carbon (PyC) layer. The orthogonal cutting experiments of 2.5D C/SiC composite with high-speed photography technology is carried out. The results show that the proposed model can accurately predict the microscopic deformation and fracture of the fiber. Meanwhile, surface fiber spring-back phenomenon is found based on high-speed photography, and its mechanism is first explanation based on the stress evolution analysis of the multi-scale model. In addition, it indicates that the increase of the depth of cut has a significant impact on the chip shape evolution, transitioning from powdery, needle-like, to block-like or strip-like shape. The paper covers some new sights for low-damage cutting of 2.5D C/SiC composite materials.

Carbonized polyacrylonitrile-coated three-dimensional porous TiP2O7 as a high-rate capability anode for lithium-ion batteries

TiP2O7 is a hopeful anode material for lithium-ion batteries (LIBs) due to its three-dimensional (3D) open skeletons, excellent ion transfer kinetics, and good structural stability. However, the inferior intrinsic electronic conductivity degrades seriously the electrochemical performance of LIBs. Herein, a strategy of carbonized polyacrylonitrile-coated TiP2O7 (TPO/cPAN) with 3D porous structures was proposed to enhance Li+-storage capability. The TPO/cPAN modified with 30 wt% polyacrylonitrile and calcined at 800 ℃ delivers superior long-term cycling stability at 0.5 A g−1 and excellent rate capacities of 558.7, 523.8, 477.5, 409.8, and 303.4 mAh g−1 at 0.1, 0.2, 0.4, 0.8, and 1.6 A g−1, respectively. Structural characterizations and electrochemical analysis reveal that the pyrolytic N-doped carbon layer markedly ameliorates the electron transferability and protects the electrode from organic electrolyte erosion. Meanwhile, the design of 3D porous structures and the generation of rich oxygen defects facilitate Li+ transport and pseudocapacitance energy storage. The work provides a novel pathway for optimizing the electron/ion migration of polyanionic electrode materials.

Additive manufacturing of high-performance CCF/SiC composites under dual protection

In this work, chopped carbon fibre reinforced silicon carbide (CCF/SiC) composites were fabricated by selective laser sintering (SLS) combined with reaction melt infiltration (RMI), using the SiC interface and pyrolytic carbon layer as a dual protection to protect the CCF from the erosion of molten silicon. The pyrolytic carbon layer encapsulates the CCF@SiC and the outer carbon preferentially reacts with silicon to form a β-SiC layer, which hinders the reaction of liquid silicon to CCF. Moreover, the fine-crystal β-SiC generated by the Si–C reaction optimizes the microstructure and enhances the mechanical performance of CCF/SiC composites. The CCF under the dual protection maintains its original high strength and high modulus, and the toughness of the CCF/SiC composites is significantly improved through the fibre debonding and fibre pull-out mechanism. The bending strength and toughness of CCF/SiC composites are 265.2 MPa and 3.5 MPa m1/2, respectively. The insights gained from this study contribute to a better understanding of microstructural engineering in SLS&RMI-fabricated CCF/SiC composites. This paves the way for future breakthroughs in composite material design and low-cost manufacturing for extreme environments.

Micromechanical properties of TRISO coatings by in-situ high temperature nanoindentation and microcantilever fracture

Coated nuclear fuel particles, most commonly tri-structural isotropic (TRISO), are intended for use in advanced high temperature reactors. It is vital to understand the mechanical properties of each coating layer to accurately predict the performance of these fuel particles and how these might change at each stage of their lifecycle. This paper reports results of in-situ nanoindentation, with an emphasis on the structural SiC layer, along with microcantilever testing of the critical SiC-IPyC interface. At 1000 °C the hardness of the SiC layer is ~75% lower than at room temperature implying significantly more plasticity at the reactor operating temperature. The elastic modulus was slightly lower at 1000 °C than at room temperature. Microcantilever fracture at the SiC-IPyC interface shows that failure occurs within the pyrolytic carbon layer rather than an interfacial “debonding” with a strength similar to that of bulk pyrolytic carbon.

Accelerated thermal property mapping of TRISO advanced nuclear fuel

TRistructural ISOtropic (TRISO) fuel is a leading-edge nuclear fuel form representing a departure from the more traditional nuclear fuel forms utilized in the reactor fleet of today. Rather than a monolithic fuel pellet of uranium dioxide, integral fuel forms containing TRISO fuel are composed of thousands of microencapsulated uranium-bearing fuel kernels and individually coated with multiple layers of pyrolytic carbon and silicon carbide. These multilayered ceramic coatings serve as an environmental barrier to ensure radioactive and chemically reactive fission products are contained within the reactor fuel elements, but also participate in the transfer of heat generated in the nuclear fuel to the coolant – the primary purpose of a nuclear reactor. Since traditional thermal property measurement techniques, such as laser flash analysis, would be unable to resolve the thermal properties of the individual TRISO coating layers, a simplified frequency-domain thermoreflectance technique has been developed to rapidly map the thermal properties of TRISO particles. Using this technique, the thermal properties of TRISO particles have been mapped from room temperature up to 1000 °C to examine the spatial variation and temperature-dependency of the thermal properties within each layer. Additionally, spatial-domain thermoreflectance was used to examine the anisotropy of the thermal properties for each layer at different locations within a single TRISO particle, and across multiple TRISO particles to assess the intra- and inter-particle uniformity of thermal properties, respectively. To elucidate the underlying causes for the measured variations in thermal properties, scanning electron microscopy and Raman spectroscopy were used to examine variations in microstructure and chemical bonding within the different coating layers. Results from this work are then compared with previous examinations of TRISO fuel particles and microstructurally driven mechanisms for the variations in the measured thermal properties of the different carbonaceous layers are discussed.

Effect of various methods of pre-treatment of carbon fibers on the mechanical properties of PIP-based ceramics/carbon composites

The purpose of the work was to determine the conditions of CF preparation to obtain carbide composites with favorable mechanical response. The relationships between the interfacial properties of fiber/polymethylsiloxane composite, and mechanical properties of the resulting fiber/carbide composites were investigated. The CF/resin interfacial strength was modified by oxidation of CF surface with nitric acid, silanization, and depositing CNT or a pyrolytic carbon layer (PyC). The study of composite interphases (ILSS and SEM) and surface tests of the modified CF (XPS, FT-IR, wettability measurements) showed different nature of the bonding occurring at the fiber/resin and fiber/ceramics boundary. The CF silanization significantly improved the ILSS between CFs and resin by 38.5%, while reduced flexural properties of carbide composites. The most promising treatment method of CF for PIP-based ceramic composites was modification with PyC, which provided 2 times higher ILSS, 1.5 times higher flexural strength and improved work to fracture (WF) as compared to unmodified CF.

Microsized Silicon/Carbon Composite Anodes through In Situ Polymerization of Phenolic Resin onto Silicon Microparticles for High-Performance Lithium-Ion Batteries

Silicon (Si) has been gradually explored as a next-generation anode material to replace traditional graphite anodes in lithium-ion batteries (LIBs) due to its high specific capacity (3579 mAh g–1 at room temperature). In terms of cost and tap density, silicon microparticles (SiMPs) are more advantageous than silicon nanoparticles (SiNPs) in high energy density LIBs, but they are also plagued by the more serious volume effect. Here, we design a silicon/carbon (Si/C) composite anode through the in situ polymerization of phenolic resin (PF) onto SiMPs, and after pyrolysis, SiMPs are tightly coated with pyrolytic carbon layers. When applied in LIBs, the composite anodes (μSi@PF) exhibit excellent cycling performance (1283 mAh g–1 after 400 cycles at 2 A g–1) and rate performance (a reversible capacity of about 1000 mAh g–1 at 8 A g–1). The full cell with lithium iron phosphate cathodes and μSi@PF anodes can maintain 87.7% capacity retention after 100 cycles. The great electrochemical performance can be ascribed to the rational structure design of μSi@PF in which PF pyrolytic carbon as a shell around SiMPs can accommodate the volume change of SiMPs during cycling and reduce the internal impedance. This is the first attempt to construct Si/C composites by in situ polymerizing PF resin onto SiMPs, and the great performance of Si/C anode provides a reference for the practical application of SiMPs.

Defossilization and decarbonization of hydrogen production using plastic waste: Temperature and feedstock effects during thermolysis stage

The replacement of natural gas with plastic-derived pyrolysis gas can defossilize H2 production, while subsequent capture, utilization and storage of carbon in a solid form can decarbonize the process. The objective of this study was to investigate H2 production from three types of plastics using a process comprising pyrolysis (600 °C) and thermolysis stages (1200–1500 °C). Depending on the plastic feedstock and thermolysis temperature, the laboratory-scale setup generated 1000–1350 mL/min product gas with H2 purity of 74.3–94.2 vol%. The recovery of 5–9 wt% molecular H2 per mass of plastics was achieved. Other products included solid residue (0.1–12 wt%) and oil (8–52 wt%) from the pyrolysis reactor, solid carbon (36–53 wt%) and gas impurities (2–16 wt%) from the thermolysis reactor. The purity of H2 gas was detrimentally influenced by polyethylene terephthalate in the feedstock due to the dilution of gas by CO. The decomposition of methane containing in the pyrolysis gas was the limiting reaction step during H2 production and improved at higher thermolysis temperature. Three solid carbon structures were formed during the thermolysis stage regardless of the plastic type: carbon black aggregates, carbon black aggregates coated with a layer of pyrolytic carbon and a carbon film on the inner reactor wall. Among the three types of carbon, the highest valorization potential was identified for carbon black aggregates. Plastic feedstock composition had little if any effect on carbon black properties, while high thermolysis temperature (1500 °C) reduced the particle sizes and increased the surface area of aggregates.

Effect of residual pore structure on the performance of TRISO particle fuel

The thermal-mechanical performance of tri-isotropic (TRISO) particles with residual pores used in light water reactors (LWRs) was investigated. The effect of residual pore structure on the stress distribution of the inner dense pyrolytic carbon (IPyC) layer, SiC layer, and outer dense pyrolytic carbon (OPyC) layer was studied. The dimensional changes and fission gas release of the fuel particle layers were calculated. Residual pores on the SiC layer can affect the stress distribution of the coated layers. The residual pores, especially the tetrahedrons, may be the source of cracks in the SiC layer, which can break or cause the loss of the capacity of the SiC layer. Residual pores have little influence on the stress distribution of the IPyC and OPyC layers.

Proposal of two parameters to evaluate in-situ apparent toughness of interphase in fiber reinforced ceramic matrix composites: Three-dimensional finite element simulations

Interphase structure characters such as single-layer interfacial thickness or number of multilayers may have a great influence on mechanical properties of continuous fibers reinforced ceramic matrix composites (CFRCMCs). However, the determination of the optimal interphase is still unclear for the complex microstructures of CFRCMCs. In this study, a novel Finite Element Method (FEM) -based numerical method considering mean scalar stiffness degradation and mean damage dissipation energy are proposed to quantitatively assess the effect of above structure characters on in-situ toughness of interphase. The proposed method has successfully applied on single pyrolytic carbon (PyC) layer and alternating silicon carbide/pyrolytic carbon (SiC-PyC) n multilayer systems. The results suggest that thicker PyC interphase will prone cause brittle fracture with lower toughness, whilst more layers with the same total thickness will improve fracture toughness for (SiC-PyC) n system. On the contrary, more layers with the same sublayer thickness will decrease in situ apparent fracture toughness. The proposed method explains well the previous contradictory experimental observations.

AGR-2 irradiated TRISO particle IPyC/SiC interface analysis using FIB-SEM tomography

The morphology in the interface region between the inner pyrolytic carbon layer (IPyC) and silicon carbide (SiC) layers in tristructural-isotropic (TRISO) particle fuel from the AGR-2 irradiation experiment were studied using focused ion beam-scanning electron microscopy tomography. This work quantitatively described the interface and corresponding relevant metrics to understand how the microstructural features at the IPyC/SiC interface may influence actinide and fission product interactions with the SiC layer. Particles were selected with varied 110mAg retention rates, and their volumes were reconstructed and analyzed for distributions of pores, fission product/actinide features, SiC, and IPyC. It was found that porosity accommodates fission products in the interface and SiC layers. The largest fission product/actinide precipitates were found in the interface region. This was also where the largest number fraction of fission products/actinides was found, consistent with SEM showing fission product/actinide pileup along selected areas of the interface region.

Effects of density and heat treatment of C/C preforms on microstructure and mechanical properties of C/C–SiC composites

AbstractTwill multidirectional carbon‐fiber‐reinforced carbon and silicon carbide composites (i.e., C/C–SiC) were prepared via chemical vapor infiltration combined with reactive melt infiltration process. The effect of heat treatment (HT) on the microstructure and mechanical properties of C/C–SiC composites obtained by C/C preforms with different densities was thoroughly investigated. The results show that as the bulk density of C/C preforms increases, the thickness of the pyrolytic carbon (PyC) layer increases and open pore size distribution narrows, making the bulk density and residual silicon content of C/C–SiC composites decrease. Moreover, the flexural strength and tensile strength of the C/C–SiC composites were improved, which can be attributed to the increased thickness of the PyC layer. The compressive strength reduces due to the decrease of the ceramic phase content. HT improves the graphitization degree of PyC, which reduces the silicon–carbon reaction rate and thereby the content of the SiC phase. HT induces microcracks and porosity but not obviously affects the mechanical properties of C/C–SiC composites. However, the negative impact of HT can be compensated by the increased density of the C/C preforms.

Microstructure of irradiated AGR TRISO particle buffer layers as measured by X-ray computed tomography

Shrinkage of the initially low-density buffer layer in tristructural isotropic (TRISO) coated fuel particles during irradiation is a well-known phenomenon with potential implications for fission product and actinide transport, as well as potential pyrocarbon fracture that in some cases has been observed to impact particle performance. During post-irradiation examination, the buffer layer's structure is commonly determined using 2D microscopy of a particle cross section or a series of particle cross sections at staggered depths. Although these methods provide a general idea of the irradiated buffer microstructure, they do not provide a full picture of the TRISO coating microstructure. By contrast, x-ray computed tomography (XCT) provides full 3D imaging of the TRISO particle. Particles from various compacts irradiated for the Advanced Gas Reactor Fuel Development and Qualification Program were imaged using XCT. Some of these particles were selected because of abnormal fission product inventories (e.g., low 137Cs), whereas others were randomly selected from the center of the fission product inventory distribution. Qualitative and quantitative analysis techniques were applied to the randomly selected particles as representatives of typical TRISO behavior to study the post-irradiation structure of the buffer layer. These results showed that, while separation of the buffer and inner pyrolytic carbon layers was a common behavior during the radiation-induced shrinkage of the buffer, a portion of the original buffer/inner pyrolytic carbon interface remained intact throughout irradiation in nearly all cases. These results also indicated clear trends in the degree of buffer densification with irradiation temperature and fluence.

Physics Evaluation of Alternative Uranium-Based Oxy-Carbide Annular Fuel Concepts for Potential Use in Compact High-Temperature Gas-Cooled Reactors

Abstract Lattice physics calculations have been carried out to evaluate the performance and safety characteristics of a modified high temperature gas-cooled reactor (HTGR) prismatic fuel block concept, based on the MHTGR-350 benchmark problem. Key changes were to replace the conventional tri-structural isotropic (TRISO)-filled fuel compacts with heterogeneous, multilayer annular fuel pellets made with UCO, ThCO, or (U,Th)CO. These fuel pellets have multiple protective cladding layers of pyrolytic carbon and silicon carbide, which will give it robust qualities. With the increased loading of U-235 in the fuel block, it was necessary to replace up to 78 fuel holes and 42 coolant holes with a hydrogen-based moderator (7LiH), in order to ensure a thermal neutron energy spectrum in the lattice. Calculation results demonstrate that the modified fuel concept has several advantages and some challenges relative to the conventional MHTGR-350 design concept. With the increased uranium loading and the reduced neutron leakage due the use of 7LiH moderator rods, higher burnup levels and lower natural uranium consumption levels can be achieved with the same level of uranium enrichment. In addition, the expected fuel residence time increased by a factor of 20 or more, making such a concept very attractive for use in small, modular, “nuclear battery” HTGRs that would only need to be fueled once. Calculation results for the current concept indicate positive graphite and hydrogen moderator temperature coefficients, and further modifications will be required to ensure a negative power coefficient of reactivity.

Improved mechanical strength and oxidation resistance of SiC/SiC-MoSi2-ZrB2 coated C/C composites by a novel strategy

To obtain silicon-based ceramic coated C/C composites with excellent mechanical and antioxidative properties, a SiC/SiC-MoSi2-ZrB2 composite ceramic coating was designed and prepared on the surface of C/C composites by a three-step process. Firstly, a pyrolytic carbon (PyC) layer was deposited on the C/C substrate to fill its holes and cracks. Secondly, a SiC porous layer was fabricated on the PyC layer to create many holes subsequently used to distribute massive MoSi2-ZrB2 ceramics. Finally, a double-layer SiC/SiC-MoSi2-ZrB2 composite ceramic coating was formed on C/C composites after a pack cementation (PC) process, which consisted of a dense SiC inner coating (a thickness of ~ 80 µm) and a uniform and rich MoSi2-ZrB2 outer coating (~ 200 µm). The bending strength of the SiC/SiC-MoSi2-ZrB2 coated C/C sample was 21.5 % higher than that of the raw C/C sample. Moreover, the SiC/SiC-MoSi2-ZrB2 coating provided good oxidation protection for C/C composites at high temperature, and its mass loss was only 0.56 % after oxidation for 305 h at 1773 K in air due to the blocking effect of the compound oxide glass (SiO2, ZrO2 and ZrSiO4) layer on oxygen diffusion into the internal coating and C/C substrate. Therefore, this novel strategy for coating preparation can obtain SiC/SiC-MoSi2-ZrB2 coated C/C composites with excellent mechanical and oxidation resistance properties.

Structural properties of the fiber –matrix interface in carbon-fiber/carbon-matrix composites and interfaces between carbon layers and planar substrates

Abstract The structure of the fiber –matrix interface region of carbon-fiber/carbon-matrix (C/C)-composites, which is important for the mechanical properties of a composite, was studied by transmission electron microscopy. The pyrolytic carbon matrix was obtained by chemical vapor infiltration of carbon fiber preforms with different fiber architecture and fiber types. While the texture of the carbon matrix can be controlled by the infiltration conditions, the carbon texture at the fiber –matrix interface differs from the bulk matrix and cannot be determined by the infiltration parameters. We often observe a high-textured layer with a thickness up to 100 nm at the interface prior to the formation of the bulk matrix with a lower texture. The fiber –matrix interface properties of C/C-composites are compared with the interface of pyrolytic carbon layers deposited on planar Si-, BN- and cordierite-substrates. In contrast to BN-substrates, thin high-textured pyrolytic layers are observed at the interface of carbon on planar Si- and cordierite-substrates where strong bonding between pyrolytic carbon and the substrate is achieved by the formation of Si-C bonds. Stress-induced ordering is discussed as a mechanism for the formation of the high-textured interface layers.

Radial growth kinetics of epitaxial pyrolytic carbon layers deposited on carbon nanotube surfaces by non-catalytic pyrolysis

Chemical vapor deposition of pyrolytic carbon (PyC) onto carbon nanotube (CNT) surfaces by hydrocarbon pyrolysis can thicken the nanotube diameter until the desirable size. Vapor-induced thickening of CNTs may require no metal catalysts because the CNT-templated growth can easily convert PyC deposits into epitaxial graphene shells. However, little work has been done on the kinetics of the vapor-induced CNT thickening process during the non-catalytic pyrolysis. In this study, we discuss the growth mechanism of epitaxial PyC layers on CNT surfaces achieved by the low-pressure (≤1.5 kPa) pyrolysis of ethylene, which is distinct from previous studies using much higher gas pressures (4–100 kPa) for the PyC deposition. The average thickness of deposited PyC layers is calculated by analyzing the transmission electron microscopy images of PyC-coated CNTs. The crystallinity of PyC-coated CNTs is evaluated by Raman spectroscopy and X-ray diffraction. The thickness of PyC layers on CNT surfaces can be adjusted by simply changing the growth time under typical pyrolysis parameters (800 °C-1.5 kPa of ethylene). We find a two-stage nonlinear behavior to describe the growth kinetics of PyC layers, indicating that the radial growth rate of PyC layers can be influenced by the number of surface active sites. This study reveals the self-assembly mechanism of graphitic layers on the CNT template, which is expected to promote the diameter-controlled synthesis of CNTs.