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Low-Temperature CVD Graphene Nanostructures on Cu and Their Corrosion Properties.

ABSTRACT: Chemical vapor deposition (CVD) graphene is reported to effectively prevent the penetration of outer factors and insulate the underneath metals, hence achieving an anticorrosion purpose. However, there is little knowledge about their characteristics and corresponding corrosion properties, especially for those prepared under different parameters at low temperatures. Using electron cyclotron resonance chemical vapor deposition (ECR-CVD), we can successfully prepare graphene nanostructures on copper (Cu) at temperatures lower than 600 °C. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and potentiodynamic polarization measurements were used to characterize these samples. In simulated seawater, i.e., 3.5 wt.% sodium chloride (NaCl) solution, the corrosion current density of one graphene-coated Cu fabricated at 400 °C can be 1.16 × 10^-5 A/cm², which is one order of magnitude lower than that of pure Cu. Moreover, the existence of tall graphene nanowalls was found not to be beneficial to the protection as a consequence of their layered orientation. These correlations among the morphology, structure, and corrosion properties of graphene nanostructures were investigated in this study. Therefore, the enhanced corrosion resistance in selected cases suggests that the low-temperature CVD graphene under appropriate conditions would be able to protect metal substrates against corrosion.

SUBMITTER: Huang WH

PROVIDER: S-EPMC6213400 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Low-Temperature CVD Graphene Nanostructures on Cu and Their Corrosion Properties.

Huang Wei-Hao WH Lin Cheng-Hsuan CH Lin Ben-Son BS Sun Chia-Liang CL

Materials (Basel, Switzerland) 20181015 10

Chemical vapor deposition (CVD) graphene is reported to effectively prevent the penetration of outer factors and insulate the underneath metals, hence achieving an anticorrosion purpose. However, there is little knowledge about their characteristics and corresponding corrosion properties, especially for those prepared under different parameters at low temperatures. Using electron cyclotron resonance chemical vapor deposition (ECR-CVD), we can successfully prepare graphene nanostructures on coppe ...[more]

PMID: 30326613

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Project description:Due to its outstanding properties, graphene has emerged as one of the most promising 2D materials in a large variety of research fields. Among the available fabrication protocols, chemical vapor deposition (CVD) enables the production of high quality single-layered large area graphene. To better understand the kinetics of CVD graphene growth, multiscale modeling approaches are sought after. Although a variety of models have been developed to study the growth mechanism, prior studies are either limited to very small systems, are forced to simplify the model to eliminate the fast process, or they simplify reactions. While it is possible to rationalize these approximations, it is important to note that they have non-trivial consequences on the overall growth of graphene. Therefore, a comprehensive understanding of the kinetics of graphene growth in CVD remains a challenge. Here, we introduce a kinetic Monte Carlo protocol that permits, for the first time, the representation of relevant reactions on the atomic scale, without additional approximations, while still reaching very long time and length scales of the simulation of graphene growth. The quantum-mechanics-based multiscale model, which links kinetic Monte Carlo growth processes with the rates of occurring chemical reactions, calculated from first principles makes it possible to investigate the contributions of the most important species in graphene growth. It permits the proper investigation of the role of carbon and its dimer in the growth process, thus indicating the carbon dimer to be the dominant species. The consideration of hydrogenation and dehydrogenation reactions enables us to correlate the quality of the material grown within the CVD control parameters and to demonstrate an important role of these reactions in the quality of the grown graphene in terms of its surface roughness, hydrogenation sites, and vacancy defects. The model developed is capable of providing additional insights to control the graphene growth mechanism on Cu(111), which may guide further experimental and theoretical developments.

Project description:The formation and crystal structure of the binary Cu3As phase have been re-investigated. Some physical properties were then measured on both single crystal and polycrystalline bulk. Cu3As melts congruently at 835 °C. At room temperature (RT), this compound has been found to crystallize in the hexagonal Cu3P prototype (hP24, P63cm) with lattice parameters: a = 7.1393(1) Å and c = 7.3113(1) Å, rather than in the anti HoH3-type (hP24, P-3c1) as indicated in literature. A small compositional range of 74.0-75.5 at.% Cu (26.0-24.5 at.% As) was found for samples synthesized at 300 and 400 °C; a corresponding slight understoichiometry is found in one out of the four Cu atomic sites, leading to the final refined composition Cu2.882(1)As. The present results disprove a change in the crystal structure above RT actually reported in the phase diagram (from γ' to γ on heating). Instead, below RT, at T = 243 K (-30 °C), a first-order structural transition to a trigonal low-temperature superstructure, LT-Cu3-xAs (hP72, P-3c1) has been found. The LT polymorph is metrically related to the RT one, having the c lattice parameter three times larger: a = 7.110(2) Å and c = 21.879(4) Å. Both the high- and low-temperature polymorphs are characterized by the presence of a tridimensional (3D) uncommon and rigid Cu sublattice of the lonsdaleite type (Cu atoms tetrahedrally bonded), which remains almost unaffected by the structural change(s), and characteristic layers of triangular 'Cu3As'-units (each hosting one As atom at the center, interconnected each other by sharing the three vertices). The first-order transition is then followed by an additional structural change when lowering the temperature, which induces doubling of also the lattice parameter a. Differential scanning calorimetry nicely detects the first low-temperature structural change occurring at T = 243 K, with an associated enthalpy difference, ΔH(TR), of approximately 2 J/g (0.53 kJ/mol). Low-temperature electrical resistivity shows a typical metallic behavior; clear anomalies are detected in correspondence to the solid-state transformations. The Seebeck coefficient, measured as a function of temperature, highlights a conduction of n-type. The temperature dependence of the magnetic susceptibility displays an overall constant diamagnetic response.

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Low-Temperature CVD Graphene Nanostructures on Cu and Their Corrosion Properties.

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Low-Temperature CVD Graphene Nanostructures on Cu and Their Corrosion Properties.

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