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Two complementary modeling approaches (1D and 2D) are developed to explain the temperature-dependent growth kinetics of PECVD graphene formation on cobalt substrate. The gas temperature and the species concentrations are predicted for different process conditions by involving gas-phase and surface reaction mechanisms which consist of 15 gas species, 43 gas reactions, 10 surface species and 34 surface reactions. The influence of the growth temperature, the microwave power and the methane flow rate, affecting the gas species mole fractions in the reactor and the surface coverage is evaluated. The numerical results clearly indicate that the hydrogen atoms play an important role in the graphene growth in microwave plasma systems. A global sensitivity analysis is then performed in order to understand the basic mechanisms that lead to the transport of reactants by gas diffusion from the main gas stream through the boundary layer providing insight regarding the growth of graphene on the cobalt substrate.

In this paper, we report on a modified arc process to synthetize graphene, copper and zinc oxide graphene hybrids. The anode was made of pure graphite or graphite mixed with metals or metal oxides. After applying a controlled direct current, plasma is created in the interelectrode region and the anode is consumed by eroding. Continuous and abundant flux of small carbon, zinc or copper species, issued from the anode at a relatively high temperature, flows through the plasma and condenses in the vicinity of a water-cooled cathode leading to few-layered graphene sheets and highly ordered carbon structures. When the graphite rod is filled with copper or zinc oxide nanoparticles, few layers of curved graphene films were anchored with spherical Cu and ZnO nanoparticles leading to a one-step process synthesis of graphene hybrids, which combine the synergetic properties of graphene along with nanostructured metals or semiconducting materials. The as-prepared samples were characterized by Raman spectroscopy, X-ray diffraction (XRD), spatially resolved electron energy loss spectroscopy (EELS), energy filtered elemental mapping and transmission electron microscopy (TEM). In addition to the experimental study, numerical simulations were performed to determine the velocity, temperature and chemical species distributions in the arc plasma under specific graphene synthesis conditions, thereby providing valuable insight into growth mechanisms.

We performed numerical simulations to determine the effect of the most influential operating parameters on the performance of a radio frequency (RF) induction-heating system in which RF magnetic fields inductively heat metal foils to grow graphene. The thermal efficiency of the system depends on the geometry as well as on the materials’ electrical conductivity and skin depth. The process is simulated under specific graphene and two-dimensional (2D) materials growth conditions using finite elements software in order to predict the transient temperature and magnetic field distribution during standard graphene and 2D materials growth conditions. The proposed model considers different coil Helmholtz-like geometries and 11 metal foils, including Ag, Au, Cu, Ni, Co, Pd, Pt, Rh, Ir, Mo, and W. In each case, an optimal window of process variables ensuring a temperature range of 1035 °C–1084 °C or 700 °C–750 °C suitable for graphene and MoS2 growth, respectively, was found. Temperature gradients calculated from the simulated profiles between the edge and the center of the substrate showed a thermal uniformity of less than ∼2% for coinage metals like Au, Ag, and Cu and up to 7% for Pd. Model validation was performed for graphene growth on copper. Due to its limited heat conductivity, good heating uniformity was obtained. As a consequence, full coverage of monolayer graphene on copper with few defects and a grain domain size of ∼2 µm was obtained. The substrate temperature reached ∼1035 °C from ambient after only ∼90 s, in excellent agreement with model predictions. This allows for improved process efficiency in terms of fast, localized, homogeneous, and precise heating with energy saving. Due to these advantages, inductive heating has great potential for large-scale and rapid manufacturing of graphene and 2D materials.

International audience; In this article, we report on some of the fundamental chemical and physical processes responsible for the deposition of graphene by microwave plasma-enhanced chemical vapor deposition (PECVD). The graphene is grown by plasma decomposition of a methane and hydrogen mixture (CH 4 /H 2) at moderate pressures over polycrystalline metal catalysts. Different conditions obtained by varying the plasma power (300-400 W), total pressure (10-25 mbar), substrate temperature (700-1000°C), methane flow rate (1-10 sccm) and catalyst nature (Co-Cu) were experimentally analyzed using the in situ optical emission spectroscopy (OES) technique to assess the species rotational temperature of the plasma and the H-atom relative concentration. Then, two modeling approaches were developed to analyze the plasma environment during graphene growth. As a first approximation, the plasma is described by spatially averaged bulk properties, and the species compositions are determined using kinetic rates in the transient zero-dimensional (0D) configuration. The advantage of this approach lies in its small computational demands, which enable rapid evaluation of the effects of reactor conditions and permit the identification of dominant reactions and key species during graphene growth. This approach is useful for identifying the relevant set of species and reactions to consider in a higher-dimensional model. The reduced chemical scheme was then used within the self-consistent two-dimensional model (2D) to determine auto-coherently the electromagnetic field, gas and electron temperatures, heavy species, and electron and ion density distributions in the reactor. The 0D and 2D models are validated by comparison with experimental data obtained from atomic and molecular emission spectra.

This article describes the significant roles of process parameters in the deposition of boron and nitrogen co-doped multi-walled carbon nanotubes via the arc-discharge process. The fabrication process is based on the vaporization of solid hexagonal boron nitride embedded in graphite cylinders in a nitrogen atmosphere with pressure varying from 350 mbar to 700 mbar and controlled current density between 150 and 420 A/cm2. Our results show the presence of significant amount of doped boron carbon nitride nanotubes in the cathodic deposit. These nanotubes have a narrow diameter distribution (20–30 nm) and a length up to 1 μm as analyzed by scanning electron microscopy and transmission electron microscopy. In addition to the experimental study, numerical simulations were performed to determine the temperature and chemical species distributions in the arc plasma under specific boron carbon nitride nanotubes synthesis conditions, thereby providing valuable insight into nanotubes growth and doping mechanisms in the arc.

Zinc oxide nanoparticles with different sizes and shapes have been synthesized in polyol using a bottom-up approach. We have studied the scale-up of the process to massively produce high quality nanoparticles of controlled size and shape. The scale-up strategy required the effective mixing of reagents using either axial or radial mixing configurations and was experimentally validated by comparing structural properties of particles obtained in a small and a large size reactor. In addition, the flow patterns in these reactors have been calculated using three-dimensional turbulent computational fluid dynamics (CFD) simulations. Our results indicate a strong connection between the flow patterns, as obtained by CFD simulations, and the size and shape of the particles. Actually, our pilot scale reactor allowed producing sample aliquots of ~50 grams with nanoparticle sizes ranging from 8 nm to 600 nm and aspect ratio varying from 1 (nanospheres) to 20 (nanorods). After their synthesis, these two nanoparticle classes have been tested as building blocks in D149-dye-sensitized solar cell (DSSC). The measured power conversion efficiency (PCE) was 4.66% for nanorods shaped particles and 4.21% for nanospheres. These values were significantly higher than the 3.90% PCE obtained with commercial Degussa VP20 ZnO nanoparticles.

We report on the design of a reactor to grow graphene via inductively heating of copper foils by radio frequency (RF) magnetic fields. A nearly uniform magnetic field induced by Helmholtz-like coils penetrates the copper foil generating eddy currents. While the frequency of the current is being rapidly varied, the substrate temperature increases from room temperature to ~1050 &deg, C in 60 s. This temperature is maintained under Ar/H2 flow to reduce the copper, and under Ar/H2/CH4 to nucleate and grow the graphene over the entire copper foil. After the power cut-off, the temperature decreases rapidly to room temperature, stopping graphene secondary nucleation. Good quality graphene was obtained and transferred onto silicon, and coated with a 300 nm layer of SiO2 by chemical etching of the copper foil. After synthesis, samples were characterized by Raman spectroscopy. The design of the coils and the total power requirements for the graphene induction heating system were first estimated. Then, the effect of the process parameters on the temperature distribution in the copper foil was performed by solving the transient and steady-state coupled electromagnetic and thermal problem in the 2D domain. The quantitative effects of these process parameters were investigated, and the optimization analysis results are reported providing a root toward a scalable process for large-sized graphene.

We report on the effect of mixing on the morphology of ultrafine zinc oxide nanoparticles synthesized via a polyol process using zinc acetate and water in a diethylene glycol medium. Three mixing strategies were considered: stirred batch, T-mixer, and impinging free jets. The particle granulometry was accessed using the transmission electron microscopy and x-ray diffraction methods. The nanoparticle size and polydispersity decreased with an increase in the local dissipated energy. In particular, the polyol process conducted in the same chemical environment at 353 K did not lead to the observation of nanoparticles in the stirred batch reactor but resulted in unconventionally small 6-nm particles in the T-mixer and impinging jet configurations. This result is apparently related to the micromixing eddy geometry described by the Kolmogorov length. The hydrodynamic flow patterns and energy dissipation were obtained from computational fluid dynamics simulations, which are essential in the design, optimization, and scale-up of the polyol process. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1708–1721, 2015

Multi-walled carbon nanotubes (MWCNTs) were grown by plasma-enhanced chemical vapor deposition (PECVD) in a bell jar reactor. A mixture of methane and hydrogen (CH4/H2) was decomposed over Ni catalyst previously deposited on Si-wafer by thermionic vacuum arc (TVA) technology. The growth parameters were optimized to obtain dense arrays of nanotubes and were found to be: hydrogen flow rate of 90 sccm; methane flow rate of 10 sccm; oxygen flow rate of 1 sccm; substrate temperature of 1123 K; total pressure of 10 mbar and microwave power of 342 Watt. Results are summarized and significant main factors and their interactions were identified. In addition a computational study of nanotubes growth rate was conducted using a gas phase reaction mechanism and surface nanotube formation model. Simulations were performed to determine the gas phase fields for temperature and species concentration as well as the surface-species coverage and carbon nanotubes growth rate. A kinetic mechanism which consists of 13 gas species, 43 gas reactions and 17 surface reactions has been used in the commercial computational fluid dynamics (CFD) software ANSYS Fluent. A comparison of simulated and experimental growth rate is presented in this paper. Simulation results agreed favorably with experimental data.

Two classes of inorganic materials such as metallic nanowires and metal oxides nanorods were synthesized using the polyol process and scaled-up to produce macroscopic quantities. Scale-up strategy was successfully built by performing the synthesis in a 15 cm diameter, 4.5 litersvolume cylindrical tank using a straight paddle impeller and a Rushton turbine. The actual yield of the synthesis is ~45 grams per batch for zinc oxide nanorods and ~20 grams per batch for cobalt nickel nanowires. Under the same rotation speed, the aspect ratio of the produced nanowires and nanorods using the Rushton turbine impeller with radial flow patterns has shown a lower aspect ratio, nanoparticle size and polydispersity. This is attributed to the increase of the local dissipated energy as spatially calculated by computational fluid dynamics (CFD) that is proposed to design, optimize and scale-up the polyol process.

Using the original thermionic vacuum arc method (TVA), carbon films with the thickness of about 2500 nm were coated on top of 200 nm tungsten films deposited on fine grain graphite substrates. The carbon/tungsten bilayers were irradiated using a terawatt laser system (TEWALAS), 360 ps and 100 fs pulse duration, 110–150 mJ pulse energy. The analysis of the selected area electron diffraction (SAED) pattern allowed the identification of rhomboedral structures corresponding to diamond. The Raman scattering measurements were also performed on the produced craters and the specific peak at 1330 cm−1 corresponding to diamond was observed. The CC sp3 bonding content increased to 39.4% in the irradiated region compared to 30.8% in the “as deposited” zone, as shown by XPS. The craters produced by the laser irradiation were morphologically studied using optical imaging and scanning electron microscopy.

The antimicrobial activity of nanoparticles (NPs) depends of the surface area in contact with microorganisms. The large surface area of the nanoparticles enhances their interaction with the microbes. In this work, a green, simple, rapid, and efficient ultrasound-assisted reduction method for silver nanoparticles (AgNP) synthesis is presented. For the synthesis, an aqueous solution of silver nitrate, ethanol, and ammonia was used. The adopted method can be easily implemented for any kind of scientific or industrial application due to its cost-effective nature. The effect of sonication time on the nanoparticle formation was investigated. Silver nanoparticles were analyzed through transmission electron microscopy and UV-vis spectroscopy. Antimicrobial additives can be incorporated in mass in different matrixes (polymeric or cellulosic), which is a convenient methodology to achieve antimicrobial activity. In this work, silver nanoparticles were incorporated in cellulose using an ultrasonic bath technique. The most important aspect of cellulose containing silver nanoparticles prepared by this method is its high antimicrobial efficiency. The microbiological study was carried out by a standard agar technique. The analysis showed that cellulose with incorporated silver nanoparticles exhibited strong antimicrobial activity against Escherichia coli bacteria. This makes it a promising antibacterial material for food packaging.

Experiments and modeling have been performed to predict the effect of gas pressure on species distribution and nanotube growth rate under specific conditions of synthesis of singlewall carbon nanotubes (SWCNTs) by arc discharge. Numerical results were compared with experiments in order to find a consistent correlation between the nanotube growth and the pressure. We used argon and helium as buffer gases with a total pressure varied between 0.1 and 1 bar. We experimentally observed that both the anode erosion rate and the Brunauer-Emmett-Teller (BET) surface area of the as produced nanotube soot material are very sensitive to the total gas pressure in the reactor

The diameter distribution of the nanotubes produced by electric-arc discharge are measured using Raman spectroscopy at various wavelengths. These measurements agree with the results provided by two other techniques: high-resolution transmission electron microscopy and x-ray diffraction. The mean tube diameter shifts more than 0.1 nm with the increase of argon in the inert atmosphere. Some argon concentrations favored the synthesis of metallic tubes with specific diameters. Furthermore, the background gas influences the macroscopic characteristics of nanotube yield and bundle size, as determined by Brunauer–Emmett–Teller surface area measurements and x-ray diffraction. The information collected on nanotube diameter and arrangement is correlated with temperatures calculated using a numerical model of the plasma generated between the two electrodes. Indeed, plasma temperature control during the production process is achieved using argon–helium mixtures as buffer gases. The variation of the gas mixture from pure argon to pure helium changes the plasma temperature and hence the nanotube diameter.

Collarets rich in single-walled carbon nanotubes (SWCNTs) have been grown using a direct current arc method. Arc process parameters such as current, pressure, and anode to cathode distance were varied experimentally and by modeling to provide an optimal working window. The best collaret yields were obtained when helium was used as a buffer gas. Mixing helium with argon in the buffer permits controlling nanotube diameters. In addition to an experimental study, a modeling approach was developed assuming local thermal equilibrium and homogenous and heterogeneous neutral chemistry. The gas-phase chemical model involves 81 neutral carbon species (C1, C2, . . ., C79, C60F, C70F) and 554 reactions with rates taken from data of Krestinin and Moravsky. Axial profiles of temperature, C atom, C2 radical, and fullerene distributions in the reactor are predicted as a function of process parameters. Carbon nanotube growth is considered by a set of surface reactions simulating open nanotube growth. Because nanotube surface chemistry is controlled by the local terminated bond and not by the bulk nanotube bond, a mechanistic approach based on the formal resemblance between the bonding and the structure of open nanotube and other carbon surfaces is proposed to explain nanotube growth. Predicted growth rates are in the range of 100 to 1000 microm/min.

International audience; The present paper reviews the different types of adsorbents that could be used for CO₂ capture from flue gases. They include carbon-based adsorbents, zeolites, molecular sieves, metal-organic frameworks, hydrotalcite-like compounds and advanced adsorbents. Their possibilities are described and confronted. In particular, it has been demonstrated that classical adsorbent materials need further functionalization or impregnation with different nitrogen-containing species in order to become suitable for CO₂ capture. The different methods for CO₂ capture by adsorption cyclic processes such as Pressure Swing Adsorption (PSA), Vacuum Swing Adsorption (PSA), Thermal Swing Adsorption (TSA), Electric Swing Adsorption (ESA) as well as the combination of TSA and chemical reaction, known as Thermal Swing Sorption-Enhanced Reaction (TSSER), are also mentioned in the cited literature.