Atomic Coupling Growth of Graphene on Carbon Steel for Exceptional

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Atomic Coupling Growth of Graphene on Carbon Steel for Exceptional Anti-Icing Performance Chunyang Duan, Yuxi Zhu, Wei Gu, Mengqi Li, Dong Zhao, Zenghua Zhao, Yunfa Chen, and Yu Wang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b04913 • Publication Date (Web): 12 Oct 2018 Downloaded from http://pubs.acs.org on October 12, 2018

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ACS Sustainable Chemistry & Engineering

Atomic Coupling Growth of Graphene on Carbon Steel for Exceptional Anti-Icing Performance Chunyang Duan, Yuxi Zhu, Wei Gu, Mengqi Li, Dong Zhao, Zenghua Zhao, Yunfa Chen, Yu Wang* State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, 1 North 2nd Street, Zhongguancun, Haidian District, Beijing100190, P.R. China Email: [email protected] KEYWORDS: graphene, carbon steel, chemical vapor deposition, anti-icing, cementite layer

ABSTRACT: Surface enrichment of regularly arranged C atoms on carbon steel (C-steel) substrates is intriguing but challenging due to the strong bonding force between C and Fe and complex C solubility in C-steel. We propose a novel strategy of introducing a supersaturated C isolating layer on the surface of C-steel to block the ceaseless C dissolution in bulk metal and directly grow graphene on C-steel through a controlled cooling process with selected C sources for the first time. The as-grown graphene films have strong atomic coupling with the adjacent Csteel substrate, and the presence of a gradient, structured cementite layer indicates a C diffusion blocking effect for the bulk. Finally, the novel composite exhibited an exceptional anti-icing ability.

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INTRODUCTION Low-cost C-steel is one of the most preferred engineering materials, and the global production exceeded 1.5 billion tons in 2016. Carburization is an ancient surface treatment for C-steels that is commonly used to alter their mechanical, wear and anti-corrosion properties.1,2 The conventional carburization process focuses on C potential-induced C diffusion in the longitudinal direction, and it is synchronously conducted to prevent a lateral enrichment of C atoms on the surface of the Csteel substrate. Benefiting from the development of CVD (chemical vapor deposition) techniques and the investigation of graphene growth mechanisms, CVD processes are tending to be more sustainable and greener, and high-quality graphene has been fabricated on various metal substrates. Moreover, the mesoscale effect revealed in the graphene growth process, i.e., the CVD parameters (e.g., temperature, pressure, catalyst composition, and nature of feedstock or substrate), adhesion energy between the graphene layer and metal catalyst, and interactions thereof, will drive novel physical properties and functionalities.3 To date, a linear dispersion at the Dirac point has been observed for Cu, Ag, Au, Ir and Pt, indicating electronic decoupling between the metal and graphene layer, and the gap between the metal and graphene is ~ 3 Å, which is characteristic of a weak, van-der-Waals-like interaction.4 On the other hand, Co, Ni, Ru, Rh and Re show a stronger interaction and shorter distance because these metals neglect non-local electronic contributions to bonding.5 However, challenges still remain in growing graphene on the most used industrial Csteel substrates due to the complex phase transition and extremely high C solubility of C-steel.6 When precipitated during a phase transition, C prefers to combine with Fe to create Fe3C, which is very stable and might hinder subsequent C segregation on the surface for nucleation.7 In addition, the absorbed C atoms on the surface of Fe cannot migrate to nuclei to grow into graphene films because of the strong bonding between Fe and C.8 Ni-based alloys have a self-healing


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resistance that prevents C atoms from diffusing into the bulk, and this property along with oxide species of Mn and Cr could be key factors for graphene growth.7 However, only a few studies have grown graphene on Ni-rich stainless steel or Ni layer-covered C-steel.7, 9-11 The thermodynamic preference for C potential induced C diffusion in depth would exist as a competition during the nucleation and then growth of graphene on the surface of C-steel substrate. We found there is a trade-off between the carburization process and large-area graphene growth. In the carburization process, the original surface of C-steel is transformed into an isolation layer to prevent C atoms from continuously dissolving into the bulk metal. Meanwhile, controlled cooling processes and grafting specific C sources along the cores are essential for directly growing graphene on C-steel. Along with the achievement of large-area graphene growth, a special cementite layer with a gradient structure that is mainly composed of Fe3C and Fe4C0.63 has been systematically demonstrated. The presence of a comparatively C-unsaturated state (Fe4C0.63) in the top layer indicates the influence of graphene on the C atom diffusion process as well as the shielded magnetism of C-steel. Most importantly, the composite surface on C-steel shows an intriguing anti-icing performance, as evidenced by in situ observations under environmental scanning electron microscopy (ESEM). This newly discovered graphene grown on C-steel can exceed the requirements of next-generation surface coating techniques and would be applicable in many industries. RESULTS AND DISCUSSION The direct growth of graphene on C-steel was performed in a home-made CVD equipment with an external liquid C source provider, gas flow controllers and a temperature control system. Figure 1a shows an optical photograph of a C-steel plate with half of the surface covered by a graphene layer. During growth, half of the C-steel plate was sealed in a quartz slot to prevent contact with


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the C source. As a result, the C-steel sample with and without a graphene coating reveals different morphologies. Compared with the pristine C-steel (the lower part), the graphene/C-steel sample (the upper part) loses the metallic luster. Scanning electron microscopy (SEM) images of the graphene coated C-steel (Figure 1b) also show that the surface roughness of the C-steel substrates increased slightly (Figure S1, Supporting Information), which might be due to phase and structure changes in the C-steel, especially in the surface layer during graphene growth. After a long period (~ 3 days) of etching with aqua regia, graphene that was directly grown on the surface of the Csteel was peeled off from the substrates without any damage (Figure S2, Supporting Information). The continuity and wrinkles in the graphene films were obvious with (Figure 1c) and without (Figure 1d) the residual Fe particles, and the energy dispersive spectroscopy (EDS) spectra (Figure 1g) obtained in the middle of the sample of Figure 1c confirmed the existence of Fe residues. The uniformity of the graphene film was also examined by transmission electron microscopy (TEM) images (Figure S3, Supporting Information), and the set of symmetric, six-fold electron diffraction spots obtained by selected area electron diffraction (SAED) confirmed the excellent crystallinity of the graphene. No obvious fractures were observed in the morphology measurements. Figure 1e shows the microscopic images of the single-layer graphene films peeled from the C-steel and transferred to a SiO2 substrate. The Raman mapping results (Figure 1f) obtained in the border area confirmed the high-quality and homogeneity of the single-layer graphene films, which had nearly identical Raman signals (Figure S4a, Supporting Information). Meanwhile, the Raman mapping on the multi-layer graphene also demonstrated its high uniformity (Figure S4b, Supporting Information). Figure 1h shows the Raman spectra of the as-prepared graphene directly obtained from the surface of the graphene/ C-steel substrates. The different numbers of layers were confirmed by the ratio of the G-2D peak intensities (IG/I2D) and the half height of the wavelength


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of the 2D peak according to previous literatures,12 and the thickness of 1, 2-3, 4 layered graphene films are confirmed as 0.9 nm, 2.2 nm, 4 nm according to AFM measurements (Figure S4e-g, Supporting Information). However, the Raman shifts in the 2D peak of graphene with different layer numbers were almost identical when tests were performed on graphene/C-steel substrates, but these results were contradicted by the variations in the patterns as the thickness increased. 13 Meanwhile, the in situ grown single-layer graphene that was transferred on the SiO2 substrate had an obvious redshift in the Raman 2D peak to ~ 2670 cm-1, which is identical to that of graphene grown on Cu and approximately 29 cm-1 smaller than that measured on a C-steel substrate (Figure S4d and S5, Supporting Information). At the same time, the Raman shifts in the G peaks for graphene with different layer numbers or measurement conditions were all the same, which indicated that the obvious shift in the 2D peak can be attributed to the strong connection between the graphene and the adjacent C-steel substrate.14,15 In order to investigate coupling relation between graphene and the adjacent C-steel, nano-scratch measurement (Figure S6, Supporting Information) were taken on graphene/C-steel The result shows that the adhesion force between graphene and the substrate reaches to 87 μN that is higher than the adhesion force of graphene/Cu or graphene/Ni interfaces.16 This interaction may appear between the C in the graphene layer and that in the C-steel substrates, which results in an “atomic coupling” state.


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Figure 1. Morphology and Raman characterization of the in situ-grown graphene on C-steel. a) Optical photograph of a C-steel plate with half the surface covered by a graphene layer. b) SEM images of graphene/C-steel c), d) SEM image of a peeled-off graphene film with c) and without d) Fe residue. e) Optical image of the graphene layer transferred on the SiO2 substrate. f) Raman mapping of the edge of the graphene film in e). g) EDS results for the graphene film with Fe residue shown in c). h) Raman spectra of graphene with different numbers of layers. i) Influences


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of the carburization time, C sources and controlled cooling rate on the quality of directly grown graphene. Figure 1i shows the influences of the carburization time,C sources and controlled cooling rate on the quality of the directly grown graphene. Due to the strong relationship of the temperature with the C solubility, as the temperature decreases, C atoms can be segregated on the surface of C-steel. However, when the temperature decreases extremely rapidly, C atoms can be interstitially dissolved in the lattice without segregation. On the other hand, C atoms tend to diffuse in the bulk substrate under furnace cooling (0.3 °C/s) with very small amounts of C atoms segregating on the surfaces, which results in an inadequate number of C atoms for nucleation, leading to the failure of graphene growth. Therefore, 1.5, 3 and 5 °C/s were chosen as the cooling rates from 950 °C to 850 °C, and the relationship between the cooling rate and graphene coverage is shown in Figure S7, Supporting Information. Microphotographs and Raman spectra show that the graphene grows as flakes with a low continuity under a lower cooling rate; otherwise, nearly full coverage was achieved with a higher cooling rate. Carburization is a process for adding C atoms into C-steel and increasing C enrichment on the surface of substrate. Without the carburization process, no graphene grew on the surface of the C-steel under the same experimental conditions (Figure S8, Supporting Information), which indicates that the intrinsic C atoms in the C-steel could not be the entire C source for graphene growth, and the C atoms migration during carburization and segregation process could be the reason for the strong atomic bonding interactions existing between the in-situ grown graphene and C-steel substrate. When growing graphene on conventional metal substrates such as Cu, Ni or Pd, various organics (gas, liquid and solid) can be used as C sources, and the quality of the as-grown graphene shows negligible differences.17-19 However, among monohydric alcohols with one to six C atoms, only 1-butanol and 1-pentanol can


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be used as proper C sources to achieve graphene growth (Figure S9, Supporting Information). Extra hydrogen is essential for growing graphene on Cu substrates, and it is considered both as an activator and etching reagent.20 However, no extra H2 is needed during the direct growth of graphene on C-steel surfaces, and the presence of extra H2 can etch the already-grown graphene layer, reducing its thickness or introducing defects (Figure S10, Supporting Information). The selectivity of the C sources and the influence of H2 are unique and could be related to the graphene growth mechanism.

Figure 2. Schematic image of graphene growth and a component analysis of the C-steel substrate. a) Schematic of the direct growth of graphene on C-steel. b) SEM image of the pearlite morphology that appeared after removing the in situ grown graphene. c) EBSD image of the phase distribution on the surface of the C-steel after graphene growth (blue: Fe-BCC, red: Fe3C, yellow: Fe4C0.63,


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inset: SEM image of the EBSD measurement area). d) C 1s spectra of the graphene/C-steel substrate from an XPS depth profiling study. e) The variation in the graphene coverage due to a further annealing process. f) Raman spectra of the graphene layers with different C labeling. In contrast to other metal substrates, Fe has a much higher C solubility. Additionally, the phase of C-steels can be transformed over a wide range under different temperatures or C contents.21 When C-steel is exposed to C-rich conditions, C atoms can be absorbed by the substrate via carburization, resulting in C-fixing cementite during the cooling process. Therefore, graphene cannot be directly grown on the surface of C-steel following either an absorption or segregation mechanism. Figure 2a shows a schematic of the process and mechanism of directly growing graphene on the surface of C-steel. Carburization is used to form the C isolation layer, and a controlled cooling process is used to facilitate nucleation. During the growth process, C-steel is first heated to a pre-setting temperature. After the injection of C sources, nucleation is achieved through a controlled cooling process due to the variation in the C solubility in C-steels with the temperature. Our results show that the optimized growth temperature (controlled cooling range) is in the range from 850 to 950 °C, and graphene cannot be grown on the surface of C-steels at a lower growth temperature (Figure S11, Supporting Information). This phenomenon might be due to the crystal structure preference for graphene growth. The crystal structure of C-steel (0.28 wt.%) transforms from BCC (body center cubic) to FCC (face center cubic), and FCC is favorable for graphene growth.7 Meanwhile, the cooling rate is crucial for the nucleation process because adequate C atoms are needed on the surface of C-steel to produce nuclei. Finally, graphene flakes grow based on the nuclei and bond with each other to form a continuous film. In this work, cooling rates of 3 and 5 °C /s between 950 and 850 ℃ result in the growth of high-quality graphene.


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To further reveal the graphene growth mechanism on C-steel, the surface layer of graphenecoated C-steel was removed through mechanical and electrochemical polishing. The exposed microstructure had a stripe pattern (Figure 2b) that originates from the eutectoid transition of austenite (due to C dissolution at high temperatures) in the surface layer of the C-steel. The low Gibbs free energy of the eutectoid transition and the nucleation and growth of cementite and ferrite layers next to each other result in pearlite with layered meso-structure (Figure S12, Supporting Information). The EDS results show a very high C concentration in the white stripes (Figure S13, Supporting Information). The electron back-scattered diffraction (EBSD) and X-ray photoelectron spectroscopy (XPS) depth profiling results for the in situ-grown graphene on C-steel samples prove the presence of cementite under the graphene layer, meanwhile, O content of the graphene grown on C-steel is slighter higher than that of graphene grown on Cu, which might be due to the presence of hydroxyl in carbon sources (Figure 2c, 2d and Figure S14, Supporting Information). The phase distribution provided in Figure 2c shows that cementite is mainly composed of Fe3C and Fe4C0.63, and the content and phase compositions of cementite vary with the depth. Fe4C0.63 and Fe3C were both detected on the upper layer adjacent to graphene; however, cementite structures gradually disappeared as the sampling spots increased in depth of around 20 μm (Figure S15, Supporting Information). The presence of a comparatively C-unsaturated state (Fe4C0.63) in the top layer and the decrease of cementite in the bulk substrate demonstrates the insufficient C diffusion. Meanwhile, visible amorphous C was detected on the in situ-grown graphene layer under a larger C source atmosphere (Figure S16, Supporting Information), which also indicates that graphene might act as a shielding layer to regulate the carburization process of C-steel. We also investigated the surface structure of the C-steel substrates that was treated in reaction conditions without a carburization process, or use of other monohydric alcohol (methanol, ethanol, 1-propanol, 1-


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hexanol) as the C sources with the same carburization time (7 min), i.e., CVD parameters that could not achieve graphene growth. The results (Figure S17, Supporting Information) revealed that no extensive presence of pearlite was observed on the substrates on which graphene could not be grown. This obvious contrast also confirms the importance of C-supersaturated pearlite layer for graphene growth on C-steel. In order to distinguish the C sources for the isolating layer with graphene growth, isotope-labeled (13C) C sources was injected into the CVD chamber after carburation process using normal C source (Figure S18, Supporting Information). The resulting 13

C graphene indicates that C-supersaturated pearlite layer is firstly achieved and serves as an

isolated layer to block the ceaseless C diffusion into the bulk substrate, then the remaining C atoms graft along the graphene nuclei to grow into graphene films. It has been reported that CVD-grown graphene films decompose at or above the growth temperature.22 We annealed the graphene-covered C-steel at 850 °C and 950 °C to investigate the C balance between graphene and the C-steel substrate. The loss of graphene films was evaluated through Raman and optical microscopic measurements (Figure S19, Supporting Information). The as-grown graphene quickly decomposed at 950 °C (Figure 2e). The graphene coverage decreased to 81% in 1 min, and rapidly dropped to 7% in 2 min, and the graphene was almost completely decomposed after 7 min. Next, a layer of graphene was grown with 13C-labeled methane on a Cu substrate and transferred to the surface of in situ-grown, multi-layer graphene fabricated by normal C sources (12C) on C-steel (inset of Figure 2e). The composite was annealed at 850 °C. The normal in-situ grown graphene (12C) and the isotope-labelled graphene (13C) showed disparate Raman shifts (Figure 2f);23 therefore, Raman mapping of the 2D peaks was used to identify the coverage of the different graphene layers (Figure S20, Supporting Information). The results revealed that graphene decomposed more slowly at lower temperatures, and the upper layer graphene (13C-


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labeled) disappeared faster than the underneath layer. The sequenced disappearance reveals that the graphene film was decomposed from the top surface layer rather than the graphene/metal interfaces. This phenomenon might be due to the difference in the C potentials around the graphene layers. Compared with the Ar atmosphere above, the supersaturated cementite layer beneath the graphene film contains a high C concentration. This can result in a detrimental C potential and cause graphene to dissolve into the adjacent C-steel substrate, resulting in the decomposition from the top to the bottom.

Figure 3. Vickers hardness, AFM and MFM characterizations of C-steel with and without in situgrown graphene. a) Vickers hardness of C-steels processed with different C sources (0 represents bare C-steel without graphene. C1-C6 indicate graphene grown with the same procedure using methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, respectively, as the C sources. C5-2 stands for C-steel with a graphene layer grown with 1-pentanol and removed with mechanical


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polishing). b)-d) AFM and MFM results of a bare C-steel plate after mechanical polishing (rolled state, b), annealed at 950 °C without C sources (annealed state, c), and graphene-coated C-steel grown with pentanol as the C source (atomic coupling state, d). e) Roughness of the C-steel samples with different states that are shown in b)-d). Scale bar: 2 μm. Carburization is commonly used to strengthen C-steels because cementite usually has a higher hardness, and we evaluated the Vickers hardness of the C-steels that were treated with the same procedure but different C sources. The results in Figure 3a reveal that the samples processed in methanol, ethanol, and 1-hexanol had 30% smaller hardness values than the original C-steel plate, which might be due to the lack of a cementite isolation layer and increased grain size after the heating and cooling process (Figure S17, Supporting Information). However, when using 1butanol and 2-pentanol as the C sources, a full pearlite isolation layer was created with the growth of high-quality graphene; therefore, a slightly higher (12%) hardness value was achieved compared with that of the rolled-state C-steel. After removing the in situ-grown graphene on the surface, Csteel substrate appeared to have a higher hardness (as much as 35%) than the untreated, bare Csteel. This might be due to the exposure of the pearlite on the surface which prevents the influence of the soft graphene layer. The trend in the hardness values with the C sources coincides with the formation of pearlite isolation layers and graphene films, except for the sample treated with 1propanol, which showed an incredibly high hardness without growing graphene. The fine structures of the 1-propanol-treated surfaces show that denser Fe3C structures were present than that observed in the other un-grown counterparts (Figure S21, Supporting Information), which might be the reason for the increased hardness. The differences in the cementite suggest the carburation ability of the C sources varies. However, carburation can be achieved with all monohydric alcohols with low C numbers; therefore, we increased the carburation times and


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attempted to grow graphene on C-steel substrates with the optimized cooling rate (5 °C /s) from 950-850 °C, using ethanol and 1-propanol as the C sources. The results (Figure S22, Supporting Information) show that graphene with a compromised continuity could be grown on C-steel with ethanol and propanol when the carburation time was increased to 1.5 h and 0.5 h, respectively, but these times are much longer than those required with 1-butanol and 1-pentanol C sources. The results demonstrate the importance of the cementite isolating layers for graphene growth on Csteel, and the graphene growth quality is highly dependent on the C source. The surface properties, including the roughness and magnetism of the C-steel plates in different states, were investigated with atomic force microscopy (AFM) and magnetic force microscopy (MFM) (Figure 3b, c, and d). As seen in Figure 3e, when annealed in a CVD chamber without C sources, the C-steel shows a negligible change in the roughness. However, the roughness grew tremendously after graphene growth, which is consistent with the SEM results (Figure 1a and Figure S1, Supporting Information). The increased roughness might be due to the phase and orientation changes that occur during growth, as revealed by EBSD results (Figure S23, Supporting Information). MFM is a widely used method for separating magnetic domains and topography. Without any treatment, a clearly magnetic domain distribution similar to a maze formation was observed on the surface of the C-steel (right image of Figure 3b), which is typical of magnetic Csteels.24,25 Annealing is thought to reduce the magnetism; however, the maze-like arrangement was obtained after the C-steel was annealed in 950 °C for 7 min, which suggests that the graphene growth temperature may not affect the magnetism (right image of Figure 3c). Finally, no mazelike patterns were observed on the graphene/C-steel, which shows that the magnetism of C-steel was not detected. This significant difference in the MFM results might be due to the isolation ability of graphene, which increases the distance between the C-steel substrate and the magnetic


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probes. Meanwhile, cementite has a lower magnetism, and the presence of a cementite layer underneath the graphene film can also shield the magnetism of C-steel.

Figure 4. Anti-icing characterization of C-steel with and without graphene. a)-f) ESEM images of frost on C-steel with (a-c) and without (d-f) graphene at -0.4 °C under saturated vapor conditions. g) Frost coverage on the surface of C-steel with and without a graphene coating. h) Contact angles of C-steel with and without a graphene coating. Scale bar: 10 μm. Frost formation on C-steel with and without a graphene coating was evaluated by environmental scanning electron microscopy (ESEM) at a temperature of -0.4 °C under saturated vapor conditions. The presence of frost/ice droplets on the substrates (Figure 4a-f) is demonstrated with a false color (blue), and the original images are attached as Figure S24, Supporting Information. As seen, the sample with a graphene coating had much rougher surfaces (Figure 4a) than its bare counterpart (Figure 4d) before testing. As the measurements proceeded, frost began to appear and assemble on the surface of the bare C-steel and spread to almost all exposure areas in less than 10 min. In contrast, only a few ice droplets appeared on the graphene/C-steel after ~20 min, and the


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coverage of the droplets hardly grew as the exposure time increased to more than 3 h, as shown in the real-time videos (Movies S1 and S2, Supporting Information). The frost coverage on each sample was calculated and is shown in Figure 4g, and the frosting rate of the C-steel and graphene/C-steel could be calculated as 415.6 μm2/min and 0.97 μm2/min, respectively. Therefore, C-steel that was covered with graphene films reveals exceptional anti-icing ability compared with its bare counterpart. Ice nucleation, ice growth, and ice recrystallization are the main steps for ice formation. Graphene-induced anti-icing property in this work might be attributed to these reasons. First, ice nucleation is hindered by the as-grown graphene films. Ice nucleation prefers to initiate at surface defects or edges due to the geometrical singularity and low free energy barrier.26 Compared to the bare C-steel, graphene/C-steel possesses notable increased surface homogeneity due to the full coverage of honeycomb-structured carbon covalent bonds, which could decrease the ice nucleation probability. Second, graphene films often present hydrophobic properties with the theoretical contact angle calculated as 95-100°, due to the pristine non-polar covalent bonds and the in-situ absorbed hydrocarbon pits.27 As shown in Figure 4h and Figure S25, the contact angle of graphene/C-steel is 107.32°, which is increased by 59.8% compared with that of bare C-steel (67.15°). The difference of the tested result and calculated contact angle value of graphene is due to the substrate effect, 28 which rises from the strong interaction between graphene film and the Csteel substrate as we analyzed above. Tilt angles (sliding angles) of water droplets on bare C-steel and graphene/C-steel were measured as 86° and 23°, respectively (Figure S26, Supporting Information). The sharply decreased tilt angle demonstrates low water adhesive force on the graphene/C-steel substrates. It is reported that the hydrophobic surface with low water adhesive force enables impacting droplets to bounce of the surface before ice nucleation, thus interfering


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with the embryo formation and icing growth.

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As shown in Figure 4a-f and the real-time

videos, the nucleation rate and the number of ice nuclei on graphene/C-steel is much slower and fewer than that on C-steel. And these relative long distances between supercooled water droplets or ice nuclei could alleviate icing accretion on graphene/C-steel because the far apart ice drops can hardly coalesce and propagation due to the missing of interbridges.26 Furthermore, water droplets on graphene/C-steel have less contact area with the solid surface due to its hydrophobic and lowadhesive ability, which hampers the heat-transfer and delays the freezing time of condensed water on graphene surface thus increasing the anti-icing ability.

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Lastly, it is reported that stacking-

disordered ice crystallites are more stable and beneficial for ice formation, however, the honeycomb hexagonal scaffold of graphene could reduce the disorder of ice crystal nuclei, which are adverse for frost or ice on surfaces. 32,33 Current

hydrophobic

ice-mitigation

layers

including

chemical-etched

patterned

nanostructures,34,35 and surface grafted or grown nanoparticles,26,30,31,36 require relatively complex and time-consuming preparation procedures, and have difficulties in realizing full coverage of the target devices. Meanwhile, the low adhesion between the surface modified nanostructures with the substrate could also lead to stability problems in low temperature or recycling. CVD process is one of the most promising way to obtain high quality graphene films directly on metal substrates in industrial scale. High quality CVD graphene could be grown completely on arbitrarily sharped surfaces without changing their original morphologies. Meanwhile, benefiting from the improvement of CVD equipment and process, CVD process is tending to be more sustainable and greener. In this work, the frosting rate on graphene/C-steel decreases 99% compared to that of bare C-steel in 3 h, which shows one of the best anti-icing performances in the recent publications.30,31,34-36


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CONCLUSIONS In conclusion, C-steel is a difficult challenge in the CVD graphene fabrication field due to its complex C solubility and phase transition. In this work, we achieved the direct growth of highquality graphene films on C-steel for the first time by introducing a C supersaturated isolating layer on the surface of C-steel to block continuous C dissolution in the bulk metal. The as-grown graphene films revealed a strong connection with the adjacent C-steel substrate and exceptionally enhanced the anti-icing ability of the novel composite. This work enriches the metal substrate species for graphene growth and provides an insight into the graphene-growth mechanism and Csteel carburization process. EXPERIMENTAL SECTION Direct growth of graphene on the surface of C-steel. C-steel substrates (electric discharge machining cutting into 20 mm×17 mm, 50 mm×30 mm, 2 mm thick, C content is 0.28%) were firstly washed in dichloromethane to remove the protection oil, then treated with mechanical polishing process to clear the rusts. After cleaning, C-steel plates were loaded into the heating zone on a quartz plate in the home-built CVD system, which consists a quartz tube, mechanical pump, gas flowmeters and liquid C sources injection system. Before growth, the furnace was firstly evacuated to lower than 20 Pa, and argon (Ar) and hydrogen (H2) were injected to wash the growth tube and remove the residue O2. Then, the furnace was heated to the pre-set temperature (600, 650, 700, 750, 800, 850, 900, 950, 1000℃) with the heating rate as 15 ℃/min. Once the desired temperatures were reached, the protection gas was stopped with the pressure of the growth tube dropped to 10 Pa, then, the liquid C sources (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol) were injected through the pressure difference between C source container and the low-pressure growth tube. The injection amount of liquid C sources was controlled by the valve


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and heating temperature (30-120 ℃) of the C source container, and monitored through the pressure of growth tube. In order to maintain the same C content in graphene growth with different C sources, the C partial pressure was controlled as 60 Pa, and the pressure of each liquid C sources could be calculated accordingly. The injection of liquid C sources was lasted in different pre-set duration (0, 3, 5, 7, 30, 90 min). Then, with the same flow rate of liquid C sources, the temperature of the furnace was dropped by 100 ℃ from the carburization temperature with the cooling rate as 0.3, 1.5, 3, 5 ℃/s, and the air cooling system was used to control the cooling rate. Finally, the furnace was cooling to room temperature under furnace cooling, and the samples were taken out for further evaluation. Peeling off the in-situ grown graphene films from C-steel substrates. Graphene film was peeled from the C-steel substrate via wet-etching process. C-steel plates were diminished to the thickness as 0.5 mm. Then graphene was directly grown on the surface with pentanol (growth temperature as 950 ℃, carburization time as 7 min, cooling rate as 5 ℃/s). Then the as-prepared graphene coated C-steel plate was fixed in a self-made plastic frame, and sealed subsequently with silicone rubber. Finally, the sealed sample was floated on the surface of etchant to ensure that aqua regia could only react with the C-steel substrate. The etchant was prepared by mixing the hydrochloric acid and nitric acid with the volume ratio as 3:1. The etching interfaces should be checked and rinsed with DI-water every 10 min until the C-steel was completely etched. It costs at least 15 h to etch the entire C-steel substrate (thickness as 0.5 mm) away. After the vanishing of C-steel substrate, graphene films could be fished out with filter paper, and transferred to the surface of fresh DI-water for cleaning for several times. At last, the clean graphene film could be transferred to different substrates for further measurements. XPS results of graphene before and after transferred from C-steel substrate show comparably consistent O fraction, which demonstrates that


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aqua regia is feasible for etching C-steel away without damaging the as-grown graphene layer. The robustness of graphene in aqua regia appeared in our experiment might be attributed to the oxidation diminishing of aqua regia in long time etching, the stable electrode potential of C in Cl-rich condition, and the sealed frame we made for keeping the graphene/C-steel sample floating on the surface of etchant during the entire etching process. Nanoscratch measurement of graphene/C-steel sample. Adhesion force of graphene on C-steel substrate was measured using Nanoscratch method for measuring adhesion at nano-scale. Nanoscratch tests were conducted in Hysitron TriboScope with 150 nm tip radius. The normal load used for scratching was 300 μN with load resolution of 1 nN. The scratch length was kept constant at 10 μm with 0.3 μm/s velocity. The data are the average of three independent measurements under identical conditions. The lateral force required to tear off the graphene film from the C-steel is defined as the adhesion force of graphene on it. The absolute value of lateral force between minimum and maximum on graphene/C-steel curve is calculated to estimate the adhesion force of graphene film. Electron back-scattered diffraction (EBSD) measurements of C-steel after graphene growth. Three kinds of C-steel samples were prepared under the treatment of graphene growth process. The surface of first sample was initially machine polished to remove the graphene. The second one was cut by electrical charge machining along the plane parallel to the surface and half away from the surface. And the third sample was also cut by electric charge machining along the crosssection of the plate. The new exposed surfaces of all three samples was electro polished using the solution of 95% acetic acid and 5% perchloric acid. In order to acquire a more flat surface, the sample was ion thinning for 4 hours by Leica RES101, which helps to acquire Kikuchi pattern of high quality. After that treatment, EBSD was measured by ZEISS ultra 55.


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XPS depth profiling study of graphene/C-steel. C1s spectra of graphene/C-steel substrate by XPS depth profiling study by PHI Quantera SXM. The specimens were ion sputtered using an argon gun operating at 3 keV to conduct in-depth profile analysis. The Argon ion beam with ∼150 μA/cm2 current density was rastered over a 2 mm×2 mm area yielding a sputter rate of ∼2.5 nm/min. XPS spectra were obtained at every 1 nm with the different depth. Atomic force microscope (AFM) and magnetic force microscope (MFM) test. C-steel in different states (rolled state, annealed state, and atomic coupling state) was tested on the same sample after different treatment. During test, a scanning probe microscope with a model of Bruker Multimode 8 was selected. The tapping/lift mode of operation was characterized by scanning the top of the sample surface twice to detect the surface of the magnetic field force data. In order to ensure that AFM and MFM can detect the surface morphology and magnetic domain structure at the same position on the C-steel during the test, the sample is marked with a larger indentation and a smaller indentation before the test. The two indentations should simultaneously appear on the page of the test window, according to the relative position of the two indentations, calibration of the location of the points to be measured. The bare C-steel is first polished to ensure that the surface roughness is low, then the AFM and MFM testing of bare C-steel samples is carried out with the test range as 20 μm and the height of the probe as 180 nm. After testing, the sample was annealed at an annealing temperature of 950 ℃ for 7 min, followed by AFM and MFM testing. The test position was selected as the same position as the first test, the scanning range is 20 μm with the height of the probe as 180 nm. Finally, the C-steel was used to grow graphene, and then directly perform AFM and MFM testing. Test position was still selected as same as the previous test position, with the scanning range as 20 μm and lift the probe height as 180 nm.


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Environmental scanning microscopy (ESEM) test. ESEM test was proceeded in QUANTA FEG 250 in the environment scan mode. C-steel with and without graphene coatings were firstly cut into 5 mm×5 mm to suit the sample stage. The test temperature was -0.4℃, the humidity in the test environment was 100%, and the magnification was ~ 5000×. The icing conditions of the samples were observed, and the real-time conditions of the icing speed and the number of icing embryo on the sample surface were recorded in real time. ASSOCIATED CONTENT Supporting Information. Figure S1 shows the SEM image of C-steel before growing graphene, and S2 shows the detailed process of peeling off the graphene film from the C-steel substrate. Figure S3 reveals the TEM images of graphene that peeled off from C-steel substrate. Figure S4 and Figure S5 show the Raman spectra of the as-grown graphene and single-layer graphene on different substrate, respectively. Figure S6 is nanoscratch measurement result on graphene/C-steel sample. Figure S7, S8, S9, S10, S11 and S16 shows the influences of cooling rate, carburization time, C source, H2 flow rate, temperature and C source flow rate to the quality of as-grown graphene, respectively. Figure S12 explains the formation of pearlite morphology. Figure S13 shows the EDS results of cementite structures. Figure S14 is the XPS depth profiling results of bare C-steel and graphene coated C-steel. Figure S15 shows the EBSD results of C-steel after graphene growth. Figure S17 reveals SEM images of C-steel substrate treated in different C sources, and the fine structures of C-steel surface that was treated in 1-propanol are shown in Figure S21. Figure S18 shows graphene that was grown with isotope-labeled (13C) C sources. Figure S19 is the microphotograph and Raman spectra of as-grown graphene coated C-steel after annealing. Figure S20 shows the Raman


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results of 13C graphene and 12C graphene coated C-steel substrate after annealing. Figure S22 is the Raman spectra of graphene that grown with ethanol and 1-propanol. Figure S23 reveals the orientations of C-steel samples in different states. Figure S24 and Figure S25 show the original ESEM images of frost formation and the contact angles on C-steel plates with and without graphene coatings. Figure S26 shows the tilt angles (sliding angles) of water droplets on bare Csteel and graphene/C-steel (PDF). Movie S1 and S2 are the short movies of ESEM testing (MP4). This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * Email: [email protected] Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21473209, 51503210), the Hundred Talents Program of the Chinese Academy of Sciences (CAS) and the State Key Laboratory of Multiphase Complex Systems Open Foundation (Grant No. MPCS-2013C-01).


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TOC

Atomic coupling grown graphene reveals strong connection with C-steel and exceptional antiicing performance, which would be beneficial for green manufacturing industry.


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Atomic Coupling Growth of Graphene on Carbon Steel for Exceptional

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