Hydrothermal synthesis of uranium dioxide and graphene composite and its application as an additive for uranium-dioxide-based accident tolerant fuel

A novel kind of composite constructed by uranium dioxide and reduced graphene oxide (RGO) was developed via a one-step hydrothermal reduction method, named as UO₂@G. The introduction of graphene oxide (GO) to the reaction system brought significant changes: in the control experiment without GO, the reductant of ethylenediamine itself could only reduce uranyl ions to mainly U₃O₈, and the final solid products appear in the form of flakes; by introducing GO to the system, the final products are pure UO₂ in homogenous nanospheres. By employing UO₂@G as an additive in the UO₂ fuel pellet (the final volume ratio of graphene materials was controlled to be around 10%), the thermal conductivity is increased by 35.4%, which is significantly higher than that of the pellet prepared by simply mixing UO₂ powders and commercial graphene nanosheets. The simulation results show that the core temperature of the pellet containing the UO₂@G composite additives is much lower than that of the one without UO₂@G composite additives, showing the potential as novel kind of accident tolerant fuel.     

In-situ synthesized nanocrystalline UO2/SiC composite with superior thermal conductivity

In this study, a novel UO₂/SiC nanocomposite pellet was constructed via in-situ hydrothermal synthesis and SPS. Such method could avoid the problem of traditional mechanical mixing that could obtained the molecular level mixing during a chemical process. Using such method, SiC was dispersed uniformly in the UO₂ matrix. Its thermal conductivity is significantly higher than those of UO₂ pellet fabricated using hydro-thermally prepared powder and traditional UO₂ pellets at both working temperature (400 °C) and near-accident temperature (1000 °C). The thermal conductivity of UO₂/SiC nanocomposite pellet increased 23.7 % over traditional UO₂ and 48.9 % over UO₂ pellet fabricated using hydro-thermally prepared powder at 400 °C. It also increased 33.6 % over traditional UO₂ and 74.8 % over UO₂ pellet fabricated using hydro-thermally prepared powder at 1000 °C. These advantages are expected to maintain high thermal conductivity of fuels, enhance heat transferring efficiency of reactors, and minimize risks of pellet failure in the entire fuel life cycle.     

Densification behaviour of UO2/Mo core-shell composite pellets with a reduced coefficient of thermal expansion

UO₂/Mo composite pellets with enhanced thermal conductivity have been considered for the novel construction of high-safety fuel systems. UO₂/Mo core-shell composite pellets with a reasonable porosity of 4–5% were fabricated by spark plasma sintering (SPS). In the SPS UO₂/Mo composite, the majority of pores remained homogeneous in the UO₂ matrix, while it had a dense morphology in the continuous Mo channel for the heat conduction. The sintering behaviour of the UO₂/Mo composite indicated that the incorporating Mo impeded densification of UO₂, and the primary densification temperature ranged from 903 K to 1270 K. To introduce 2 vol% Mo to UO₂, the thermal conductivity (TC) was enhanced to 4.02 W/m·K at 1073 K. The above result represented a 23.31% improvement over the value of 3.26 W/m·K (Fink) for a pure UO₂ pellet, which was approximated by the revised Hasselman-Johnson model. In particular, the coefficient of thermal expansion (CTE) was reduced to 10.0 × 10⁻⁶/K from 298 K to 1673 K, representing an 8.83% reduction from the value of 10.98 × 10⁻⁶/K (Martin) for a pure UO₂ pellet. The reduction effect on the CTE was superior to that of other UO₂ matrix composites fuel systems and, hence, offers an external safety aspect for reactors at the elevated temperatures close to accident conditions. These results provide a feasible method for the fabrication of a UO₂/Mo core-shell pellet as an accident tolerant fuel.     

Highly electrically and thermally conductive silicon carbide-graphene composites with yttria and scandia additives

Dense silicon carbide/graphene nanoplatelets (GNPs) and silicon carbide/graphene oxide (GO) composites with 1 vol.% equimolar Y₂O₃–Sc₂O₃ sintering additives were sintered at 2000 °C in nitrogen atmosphere by rapid hot-pressing technique. The sintered composites were further annealed in gas pressure sintering (GPS) furnace at 1800 °C for 6 h in overpressure of nitrogen (3 MPa). The effects of types and amount of graphene, orientation of graphene sheets, as well as the influence of annealing on microstructure and functional properties of prepared composites were investigated. SiC-graphene composite materials exhibit anisotropic electrical as well as thermal conductivity due to the alignment of graphene platelets as a consequence of applied high uniaxial pressure (50 MPa) during sintering. The electrical conductivity of annealed sample with 10 wt.% of GNPs oriented parallel to the measuring direction increased significantly up to 118 S·cm⁻¹. Similarly, the thermal conductivity of composites was very sensitive to the orientation of GNPs. In direction perpendicular to the GNPs the thermal conductivity decreased with increasing amount of graphene from 180 W·m⁻¹ K⁻¹ to 70 W·m⁻¹ K⁻¹, mainly due to the scattering of phonons on the graphene – SiC interface. In parallel direction to GNPs the thermal conductivity varied from 130 W·m⁻¹ K⁻¹ up to 238 W·m⁻¹ K⁻¹ for composites with 1 wt.% of GO and 5 wt.% of GNPs after annealing. In this case both the microstructure and composition of SiC matrix and the good thermal conductivity of GNPs improved the thermal conductivity of composites.     

Fabrication of a hybrid graphene/layered double hydroxide material

A hybrid graphene/Ni²⁺–Fe³⁺ layered double hydroxide material has been fabricated by the hydrothermal treatment of a mixed suspension of the exfoliated graphite oxide, Ni(NO₃)₂ 6H₂O, Fe(NO₃)₃·9H₂O, urea and trisodium citrate. The Ni²⁺–Fe³⁺ layered double hydroxide platelets are first homogeneously grown on the surface of GO nanosheets which are then reduced to graphene under a mild hydrothermal treatment. In the hybrid graphene/Ni²⁺–Fe³⁺ layered double hydroxide material, the restacking of graphene nanosheets is effectively prevented by the formation of Ni²⁺–Fe³⁺ layered double hydroxide platelets, and the graphene nanosheets exist in a complete exfoliation state.     

One-step electrosynthesis of MnO2/rGO nanocomposite and its enhanced electrochemical performance

We present a facile one-step electrochemical approach to generate MnO₂/rGO nanocomposite from a mixture of Mn₃O₄ and graphene oxide (GO). The electrochemical conversion of Mn₃O₄ into MnO₂ through potential cycling is expedited in the presence of GO while the GO is reduced into reduced graphene oxide (rGO). The MnO₂ nanoparticles are evenly distributed on the rGO nanosheets and act as the spacer to prevent rGO nanosheets from restacking. This unique structure provides high electroactive surface area (1173?m² g^?1) that improves ions diffusion within the MnO₂/rGO structure. As a result, the MnO₂/rGO nanocomposite exhibits high specific capacitance of 473?F?g^?1 at 0.25?A?g^?1, which is remarkably higher (3 times) than the Mn₃O₄/GO prior conversion. In addition, the electrosynthesized nanocomposite shows higher conductivity and excellent potential cycling stability of 95% at 2000 cycles.     

Graphene oxide-anchored reactive sulfonated copolymer via simple one pot condensation polymerization: proton-conducting solid electrolytes

A rapid and efficient post-polymerization functionalization of poly(urea-co-urethane) (PUU) onto the graphene oxide (GO) nanosheets has been developed to produce super-acidic polymer/GO hybrid nanosheets. Thus, the surface of GO nanosheets were functionalized with 3-(triethoxysilyl)propyl isocyanate (TESPIC) from hydroxyl groups to yield isocyanate functionalized graphene oxide nanosheets. Then, sulfonated polymer/GO hybrid nanosheets were prepared by condensation polymerization of isocyanate-terminated pre-polyurea onto isocyanate functionalized graphene oxide nanosheets through the formation of carbamate bonds. FTIR and TGA results indicated that TESPIC modifier agent and poly(urea-co-urethane) were successfully grafted onto the GO nanosheets. The grafting efficiency of poly(urea-co-urethane) polymer onto the GO nanosheets was estimated from TGA thermograms to be 205.9%. Also, sulfonated polymer/GO hybrid nanosheets showed a proton conductivity as high as 3.7 mS cm^?1. Modification and morphology of GO nanosheets before and after modification processes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD).     

Process intensification of uniform loading of SnO2 nanoparticles on graphene oxide nanosheets using a novel ultrasound assisted in situ chemical precipitation method

In this paper, a novel ultrasound assisted, solution-based chemical synthesis method for the preparation of SnO₂–graphene nanocomposite is presented. Graphene oxide (GO) was prepared by the modified Hummers–Offeman method in presence of ultrasonic irradiation. Further loading of SnO₂ on GO was carried out with an ultrasound assisted solution-based synthesis route. The prepared GO and SnO₂–graphene nanocomposite were characterized by XRD, TEM, FTIR spectra, TGA and DTA analysis in order to confirm the formation of graphene–SnO₂ nanocomposite. TEM analysis of ultrasonically prepared graphene–SnO₂ composite shows the uniform and fine loading of SnO₂ particles (3–5 nm) on graphene nanosheets. However agglomerated morphology was observed in case of conventionally prepared graphene–SnO₂ composite. The cavitational effects generated due to the ultrasonic irradiations during the synthesis of graphene–SnO₂ composite improve the fine and uniform loading of SnO₂ on graphene nanosheets by oxidation–reduction reaction between GO and SnCl₂·2H₂O compared to conventional synthesis methods. The formed material was used for the preparation of anode in lithium ion batteries and its electrochemical performance was characterized by cyclic voltammetry and charge/discharge cycles. It is found that the capacity of SnO₂–graphene nanocomposite based Li-battery is stable for around 120 cycles, and the battery could repeat stable charge–discharge reaction.     

Functionalized graphene‐reinforced rubber composite: Mechanical and tribological behavior study

A functionalized graphene, fluorinated graphene nanosheets (FGS), and SiO₂ nanoparticles as reinforcing fillers were employed to improve the mechanical properties of the solution styrene butadiene and butadiene rubber composites (SSBR‐BR). The results showed that the mechanical properties of SSBR‐BR composite filled with FGS were substantially improved than those of the unfilled and equivalent filler loaded graphene oxide (GO) and reduced graphene oxide (rGO) filled SSBR‐BR composites. It can be ascribed to the fact that the hydrophobic surface of FGS can be endowed the good dispersion in rubber matrix and stronger interfacial interaction between rubber and fillers. The tribological properties of these composites are also investigated. The results reveal that incorporation of GO, rGO, and FGS in SSBR‐BR composites can decrease antiwear properties because the existence of layered graphene promotes to tear and peel off. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44970.     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

In situ synthesis of ultrathin 2-D TiO2 with high energy facets on graphene oxide for enhancing photocatalytic activity

Two kinds of TiO₂ with novel structures, interpenetrating anatase TiO₂ tablets (IP-TiO₂), and overlapping anatase TiO₂ nanosheets (OL-TiO₂) with exposed {0 0 1} facets, are synthesized. The graphene oxide (GO) supported ultrathin TiO₂ nanosheets (OL-TiO₂/GO) is also prepared by one-pot hydrothermal method. The microscopic feature, morphology, phase, and nitrogen adsorption–desorption isotherms are characterized. The performance of photocatalytic degradation of methyl blue is also measured. Compared with IP-TiO₂, the OL-TiO₂ with GO possess higher photocatalytic efficiency. The GO can improve the photocatalytic property by increasing specific surface area, accelerating the separation of electron–hole pairs, as well as extending the electron life. The growth process of TiO₂ nanosheets on graphene oxide layers probably follows a step-growth mechanism with F⁻ as morphology controlling agent. The steps on the surface can improve the photocatalytic activity further due to the increase of dangling bonds of 5-coordinated Ti (Ti_5c) which are considered to be the active sites in the photocatalytic reaction.     

Effect of copper sulfate pentahydrate on the structure and properties of poly(vinyl alcohol)/graphene oxide composite films

Poly(vinyl alcohol) (PVA)/graphene oxide (GO)/copper sulfate pentahydrate (CuSO₄·5H₂O) composite films were prepared by the solution casting method, and the effect of CuSO₄·5H₂O on the structure and properties of the PVA/GO composites was investigated. Fourier transform infrared (FTIR) analysis proved the crosslinking interaction between CuSO₄·5H₂O and the ? OH group of PVA. The crystallinity of the composite films increased first and then decreased. For the composite films, the tensile strength, Young's modulus, and yield stress values improved with increasing CuSO₄·5H₂O, whereas the elongation at break decreased compared with that of the neat PVA/GO composite film. The thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG) patterns of the PVA/GO/CuSO₄·5H₂O composite films showed that the thermal stability decreased; this was consistent with the TGA–FTIR analysis. A remarkable improvement in the oxygen‐barrier properties was achieved. The oxygen permeability coefficient was reduced by 60% compared to that of the neat PVA/GO composite film. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44135.     

SiO2-covered graphene oxide nanohybrids for in situ preparation of UHMWPE/GO(SiO2) nanocomposites with superior mechanical and tribological properties

The modified Hummer technique was used in the preparation of graphene oxide (GO) nanosheets, and then SiO₂ decorated GO [GO(SiO₂)] nanosheets were synthesized via the sol–gel method. Then, ultrahigh-molecular-weight polyethylene (UHMWPE) nanocomposites loaded with 0.5, 1, 1.5, and 2 wt % of GO(SiO₂) were prepared using magnesium ethoxide/GO(SiO₂)-supported Ziegler–Natta catalysts via the in situ polymerization. Morphological study of the prepared polymer powders was assessed using field-emission scanning electron microscopy, which showed that GO(SiO₂) nanohybrids have been uniformly dispersed and distributed into the UHMWPE matrix. Also, the neat UHMWPE and its nanocomposites were evaluated with different analyses, including viscosity-average molecular weight measurement, differential scanning calorimetry, thermogravimetric analysis, tensile test, scratch hardness, and pin-on-disk test. The characterization of the UHMWPE nanocomposites indicated that many characterizations, including the mechanical, thermal, and tribological properties of UHMWPE, were significantly improved by incorporation of these new nanosheets in spite of the molecular weight reduction of the polymeric matrix and the improved flowability and processability of the produced nanocomposite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47796.     

Graphene nanosheets-tungsten oxides composite for supercapacitor electrode

Graphene nanosheets-tungsten oxides (tungsten oxide/tungsten oxide hydrate mixture) (GNS-W) composite was successfully synthesized using a facile approach. WO₃/WO₃·H₂O mixtures were deposited on the graphene nanosheets (GNS) to form the GNS-W composite. The GNS-W composite was characterized by X-ray diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-prepared GNS-W composite was directly fabricated into a supercapacitor electrode for potential energy storage application, and electrochemically tested by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The GNS-W composite electrode exhibits a better electrochemical performance than that of the WO₃/WO₃·H₂O mixtures electrode. A high specific capacitance of about 143.6 F g⁻¹ at a current density of 0.1 A g⁻¹ for the GNS-W composite delivers significant improvement than that for the WO₃/WO₃·H₂O mixtures and GNS electrodes. The impedance studies also suggest that the GNS-W composite electrode shows the lower resistance and high conductivity due to the good interaction between the graphene nanosheets and the WO₃/WO₃·H₂O mixtures. The good electrochemical performance for the GNS-W composite may be attributed to the interaction between the WO₃/WO₃·H₂O mixtures and the edges of graphene nanosheets, which increases the ion diffusion rate as well as the conductivity.     

Sub-20 nm anatase particles uniformly anchored on graphene oxide and reduced graphene oxide nanosheets and their photocatalytic oxidation and Li-ion storage capabilities

Nanosized anatase TiO₂ particles anchored on nanocarbon substrates have great potential for practical applications in high-performance lithium ion batteries and efficient photocatalysts. The synthesis of this material usually utilizes calcination to crystallize amorphous titania, which normally causes the formation of aggregates and some side effects. In this work, we demonstrated that sub-20 nm anatase particles uniformly anchored on graphene oxide and reduced graphene oxide nanosheets in aqueous solution at a temperature of 90 °C and atmospheric pressure, without further calcination. The photocatalytic oxidation activity and electrochemical properties of graphene oxide/anatase TiO₂ (GO/A) and reduced graphene oxide/anatase TiO₂ (RGO/A) were comparatively investigated. We found that GO/A showed higher photocatalytic oxidation activity than RGO/A under UV light irradiation. Graphene oxide accepted electrons and suffered reduction, which finally decreased GO/A’s photocatalytic oxidation activity to an extent similar to RGO/A. We also found that, as anode material for Li-ion battery, the specific capacity of RGO/A was nearly three times that of GO/A at the same current rate. This study will inspire better design of metal oxide/nanocarbon nanocomposites for high performance lithium ion battery and photocatalysis applications.     

In situ polymerization of polyimide‐based nanocomposites via covalent incorporation of functionalized graphene nanosheets for enhancing mechanical,thermal, and electrical properties

In this study, we report an effective method to fabricate high‐performance polyimide (PI)‐based nanocomposites using 3‐aminopropyltriethoxysilane functionalized graphene oxide (APTSi‐GO) as the reinforcing filler. APTSi‐GO nanosheets exhibit good dispersibility and compatibility with the polymer matrix because of the strong interfacial covalent interactions. PI‐based nanocomposites with different loadings of functionalized graphene nanosheets (FGNS) were prepared by in situ polymerization and thermal imidization. The mechanical performance, thermal stability, and electrical conductivity of the FGNS/PI nanocomposites are significantly improved compared with those of pure PI by adding only a small amount of FGNS. For example, a 79% improvement in the tensile strength and a 132% increase in the tensile modulus are achieved by adding 1.5 wt % FGNS. The electrical and thermal conductivities of 1.5 wt % FGNS/PI are 2.6 × 10^?3 S/m and 0.321 W/m·K, respectively, which are ～10¹⁰ and two times higher than those of pure PI. Furthermore, the incorporation of graphene significantly improves the glass‐transition temperature and thermal stability. The success of this approach provides a good rationale for developing multifunctional and high‐performance PI‐based composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42724.     

A photo-induced dissolution of UO2 sintered pellets in a simulated solution

The objective of this study is to improve the established dissolution technique of UO₂ target by using a photochemical reaction. Photo-dissolution tests of UO₂ sintered powder and pellets were carried out in a simulated nitric acid solution at about 50 °C under UV irradiation. The simulated solution consists of 2 M nitric acid containing elements such as Cs, Sr, Zr, Ru, Mo and Nd. The light source is a Hg-lamp emitting 254 nm wavelength. As results, in the dark reaction, UO₂ sintered pellets were hardly dissolved, whereas UO₂ was rapidly dissolved after 7 hours of dissolution time in the UV irradiation. The very low dissolution rate in the dark reaction was due to surface characteristics of sintered pellets: UO₂ sintered pellet is very dense and has extremely low specific surface area. However, the dissolution rate of UO₂ sintered pellet was considerably increased in the simulated solution under UV irradiation. This was attributed to the fact that ruthenium and molybdenum ions in the simulated solution could accelerate the dissolution of UO₂ under UV irradiation. Additionally, when the pulverized sintered UO₂ powder was used, the dissolution rate of UO₂ increased more rapidly than that of UO₂ sintered pellet.     

Preparation of functional reduced graphene oxide and its influence on the properties of polyimide composites

Homogeneous dispersion and strong filler–matrix interfacial interactions were vital factors for graphene for enhancing the properties of polymer composites. To improve the dispersion of graphene in the polymer matrix and enhance the interfacial interactions, graphene oxide (GO), as an important precursor of graphene, was functionalized with amine‐terminated poly(ethylene glycol) (PEG–NH₂) to prepare GO–poly(ethylene glycol) (PEG). Then, GO–PEG was further reduced to prepare modified reduced graphene oxide (rGO)–PEG with N₂H₄·H₂O. The success of the modification was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and Raman spectroscopy. Different loadings of rGO–PEG were introduced into polyimide (PI) to produce composites via in situ polymerization and a thermal reduction process. The modification of PEG–NH₂ on the surface of rGO inhibited its reaggregation and improved the filler–matrix interfacial interactions. The properties of the composites were enhanced by the incorporation of rGO–PEG. With the addition of 1.0 wt % rGO–PEG, the tensile strength of PI increased by 81.5%, and the electrical conductivity increased by eight orders of magnitude. This significant improvement was attributed to the homogeneous dispersion of rGO–PEG and its strong filler–matrix interfacial interactions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45119.     

Mechanical and thermal properties of hierarchical composites enhanced by pristine graphene and graphene oxide nanoinclusions

Epoxy resin nanocomposites incorporated with 0.5, 1, 2, and 4 wt % pristine graphene and modified graphene oxide (GO) nanoflakes were produced and used to fabricate carbon fiber‐reinforced and glass fiber‐reinforced composite panels via vacuum‐assisted resin transfer molding process. Mechanical and thermal properties of the composite panels—called hierarchical graphene composites—were determined according to ASTM standards. It was observed that the studied properties were improved consistently by increasing the amount of nanoinclusions. Particularly, in the presence of 4 wt % GO in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 15% (21%), 34% (84%), and 40% (68%), respectively. Likewise, with inclusion of 4 wt % pristine graphene in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 11% (7%), 30% (77%), and 34% (58%), respectively. Also, thermal conductivity of the carbon fiber (glass fiber) composites with 4% GO inclusion was improved 52% (89%). Similarly, thermal conductivity of the carbon fiber (glass fiber) composites with 4% pristine graphene inclusion was improved 45% (80%). The reported results indicate that both pristine graphene and modified GO nanoflakes are excellent options to enhance the mechanical and thermal properties of fiber‐reinforced polymeric composites and to make them viable replacement materials for metallic parts in different industries, such as wind energy, aerospace, marine, and automotive. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40826.     

Low-cost preparation of a conductive and catalytic graphene film from chemical reduction with AlI3

AlI₃ synthesized by I₂ and Al in ethanol was used as reductive agent to directly obtain flexible reductive graphene oxide (RGO) films with high conductivity of 5320 S/m from graphene oxide (GO) films at a low temperature of 80 °C. This reductive method has provided a low-cost and effective route for large-scale production of graphene with high catalytic activity. Structural evolution during the reduction of GO was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The RGO films served as counter electrode exhibited high electrochemical activity.