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oastm_02 | Highlights | [
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oastm_02 | • | [
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oastm_02 | The dual-layer carbon film is prepared using CDC process with subsequent CVD method. | [
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oastm_02 | The surface of the CDC layer is highly porous in structure and chemically active. | [
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oastm_02 | The CDC layer acts as a seedbed layer for the nucleation and growth of the CVD layer. | [
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oastm_02 | The dual-layer film is tested as an effective lubricating coating for SiC components. | [
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oastm_02 | Introduction | [
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oastm_02 | Because of their unique properties, such as high hardness, good corrosion resistance, and excellent chemical stability, SiC materials are widely used for tribological applications in extreme conditions [1]. | [
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oastm_02 | However, the friction and wear coefficients of SiC materials are unacceptably high in unlubricated conditions [2]. | [
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oastm_02 | To improve the tribological properties, carbon coatings such as diamond and diamond like carbon (DLC), are usually coated on such materials using chemical vapor deposition (CVD) process [3-5]. | [
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oastm_02 | A promising method for coating carbon films on SiC termed the "carbide-derived carbon" or CDC process is greatly attractive in recent years [6]. | [
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oastm_02 | In this method, SiC is treated in a chlorine-containing gas mixture at high temperature, and the Si atoms preferentially react with Cl2 and leave the system in the form of SiCl4 [7]. | [
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oastm_02 | The CDC with unique nanostructure possesses many attractive physical, mechanical, and tribological properties. | [
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oastm_02 | In particular, it is reported in recent studies that the CDC coating can afford very low friction and wear to improve the tribological performance of the carbides. | [
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} | oastm_02 | train4 | semi |
oastm_02 | Specifically, this coating can provide a friction coefficient of 0.03-0.3 and wear rate of 10-9-10-7mm3/N·m depending on the chlorination process and friction test conditions [8-10]. | [
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oastm_02 | Surprisingly, the CDC coating with high porosity (i.e.>57.2% for β-SiC [11]) shows excellent tribological properties under dry friction condition. | [
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} | oastm_02 | train4 | semi |
oastm_02 | However, unpublished studies in our group confirm that the CDC coating is helpless in lubricating for SiC materials under some conditions, including high temperature (i.e. at 300°C), water or oil lubrication and high load. | [
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oastm_02 | The lubrication failure is attributed to the high porosity and the low strength of CDC coating. | [
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oastm_02 | Further surface modification to improve the density and strength of CDC coating is urgent for extensive tribology application. | [
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oastm_02 | Although there is little pertinent research on such work to date, some information can still be obtained in some literature. | [
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oastm_02 | Grannen and Chang [12] deposited diamond films from fluorocarbon gases in microwave plasma on SiC and WC substrates without any pretreatments. | [
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oastm_02 | The proposed growth mechanism suggests that the surface carbon layer formed by the etching of carbide substrates with fluorine atomic favors the nucleation of diamond. | [
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} | oastm_02 | train4 | semi |
oastm_02 | It is reported that ultrananocrystalline diamond (UNCD) could also be deposited on the CDC films using microwave plasma CVD reactor and the tetrahedrally bonded carbon in the CDC films is suggested as a good seed for UNCD deposition [13]. | [
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oastm_02 | According to our considerations, the CDC layer which is formed by chlorination of SiC acts as a seed and intermediate layer for subsequent deposition. | [
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oastm_02 | The CVD process is operated in a same reactor using CCl4 as carbon source. | [
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oastm_02 | We used Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and field emission scanning electron microscopy (SEM) to determine the microstructure and chemistry of CDC and CVD films. | [
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oastm_02 | And friction and wear properties of the CDC and dual-layer film are discussed. | [
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oastm_02 | It is expected that this dual-layer film can provide better lubrication for SiC materials in many applications. | [
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oastm_02 | Experimental section | [
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oastm_02 | Film preparation | [
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oastm_02 | The dual-layer film was synthesized by pre-chlorination of single crystalline 6H-SiC wafer with subsequent chemical vapor deposition (CVD) using CCl4 as precursor. | [
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oastm_02 | The n-type 6H-SiC wafer (10×10mm2) with polished Si-face was purchased from TianKe Blue Semiconducter Co. | [
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oastm_02 | Ltd (Beijing, China), with nominal cut-off angle of about 0-5°. | [
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oastm_02 | The schematic process to synthesize the dual-layer film was demonstrated in Fig. 1. | [
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oastm_02 | Both the CDC process and CVD deposition were carried out in a tube furnace in turn. | [
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oastm_02 | The CDC process was described in detail elsewhere [7]. | [
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oastm_02 | In our experiments, the CDC layer was fabricated by chlorination of SiC in a gas mixture (Cl2 at a flow speed of 2mlmin-1+Ar at a flow speed of 98mlmin-1) at 1000°C for 10min. | [
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oastm_02 | The Si was preferred to react with Cl2 and removed away in the form of volatile SiCl4. | [
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oastm_02 | The surface of SiC was converted into CDC and the shape of the sample stayed unchanged, as demonstrated in Fig. 1. | [
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oastm_02 | Once the CDC process was finished, the Cl2 flow was stopped immediately. | [
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oastm_02 | Subsequently, the CCl4 was evaporated at 60°C [14] and introduced into reaction region with 50mlmin-1 Ar flow. | [
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oastm_02 | The carbon derived from pyrolyzing of CCl4 at 1000°C nucleated and grew on top of CDC layer to form the CVD layer. | [
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oastm_02 | The duration for CVD deposition was 2h. | [
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oastm_02 | The two principal chemical reactions taking place in the process included(1)SiC+2Cl2→SiCl4+Cwhich is thermodynamically allowed, with a Gibbs energy of ∆G=-434.1kJ/mol at 1000°C, and(2)CCl4→C+Cl2which is also thermodynamically allowed, with a Gibbs energy of ∆G=-36.672kJ/mol at 1000°C. | [
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oastm_02 | The carbon produced by reaction (1) formed the CDC layer, while reaction (2) formed the CVD layer. | [
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oastm_02 | As a result, the dual-layer carbon film composed of sub-layer of CDC and top layer of CVD carbon was synthesized. | [
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oastm_02 | Moreover, single CDC film was also synthesized for comparison. | [
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oastm_02 | The process parameters were the same to those in CDC process for dual-layer film preparation. | [
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oastm_02 | Characterization | [
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oastm_02 | Raman spectroscopy is a standard non-destructive analysis tool for characterization of various carbon materials. | [
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oastm_02 | The CDC and the dual-layer films were studied on a Horiba HR800 Raman system with an Ar laser excitation wavelength of 532nm. | [
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oastm_02 | This system is also equipped with a charge couple device (CCD) detector and an optical imaging for focusing the laser at a micro-region. | [
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oastm_02 | The Raman spectra were collected in the range between 600 and 2000cm-1 for 60s. | [
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oastm_02 | X-ray photoelectron spectroscopy (XPS) was used to analyze the surface composition and chemical nature of the CDC layer and the dual-layer film. | [
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oastm_02 | The XPS measurement was performed on PHI-5702 multifunctional photoelectron spectrometer, using Al-Ka X-ray (250W) as the excitation source. | [
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oastm_02 | No pre-treatment on the samples was conducted. | [
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oastm_02 | Survey spectra with energy step of 0.4eV and core level photoelectron lines C1s, O1s, Cl2p and Si2p with energy step of 0.125eV were recorded. | [
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oastm_02 | In order to investigate the surface topography evolvement, atomic force microscopy (AFM) was carried out with a Nanoscope IIIA Multimode apparatus (Veeco Instruments) under ambient conditions (relative humidity ~45%, temperature ~26-28°C). | [
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oastm_02 | AFM was performed in the tapping mode using rectangular silicon cantilevers with spring constant of ~40Nm-1 and typical resonance frequencies between 250 and 300kHz. | [
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oastm_02 | Field emission scanning electronic microscopy (FESEM, JSM-6701F) was also employed to observe the surface microstructure. | [
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oastm_02 | Friction test | [
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oastm_02 | Friction and wear behaviors of SiC, CDC layer and dual-layer film were contrastively studied on a UMT-2MT tribo-meter (CETR, USA) with a ball-on-disk configuration in ambient conditions (temperature of 27°C and relative humidity of 45%). | [
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oastm_02 | The Si3N4 and steel balls with diameter of 3mm made oscillating movement (5mm in amplitude) on the top of the samples for 30min. | [
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oastm_02 | The test conditions were 1N in load and 20mms-1 in sliding speed. | [
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oastm_02 | The friction coefficients were recorded by the tribo-meter. | [
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oastm_02 | Results and discussion | [
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oastm_02 | Raman spectrum | [
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oastm_02 | For the perfectly ordered graphite, the first-order Raman spectrum recorded in the near-infrared and visible light regimes shows only one peak around 1580cm-1, whereas disordered amorphous carbon generally exhibits two peaks: the so-called G-band at ~1580cm-1and the so-called D-band (disorder induced (D)) at ~1350cm-1, which is associated with the double-resonance Raman mechanism [15]. | [
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oastm_02 | The positions of D- and G-bands, their relative intensity ratio (ID/IG), and their full widths at half maximum (FWHM) can be used to study the structural information of the carbon materials. | [
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oastm_02 | Fig. 2 presents the Raman spectra of SiC substrate, CDC layer, and dual-layer film to investigate the structure evolvement. | [
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oastm_02 | The Raman spectrum of SiC has several peaks in the range of 800-2000cm-1. | [
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oastm_02 | The strongest peak ~968cm-1 is the longitudinal (LO) optical phonon of SiC, while the peak ~782cm-1 is the transversal optical (TO) phonon. | [
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oastm_02 | Moreover, the D- and G-bands for CDC layer are greatly broadened and cannot be fitted with two Gaussians profiles. | [
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oastm_02 | As we know, the G-peak appears due to the in-plane bond-stretching motion of pairs of sp2 bonded C atoms in graphitic compounds whatever is their stacking order or their crystallite size. | [
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oastm_02 | The broadening and shifting to high wavenumbers of the G-band can be interpreted as an increase in bond angle disorder or the ultrasmall crystal size [16]. | [
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oastm_02 | Alternatively, the internal stress induced by the nonuniformity of the crystalline structure and the mismatch between CDC and SiC substrate leads to peak broadening and up-shifting in Raman spectrum of CDC layer [17]. | [
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oastm_02 | Unfortunately, the origin of the D-band shifting toward smaller wavenumbers is unclear. | [
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oastm_02 | However, the presence of broad D-band further demonstrates the disorder structure. | [
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oastm_02 | Its large FWHM implies a large distribution of sp2 bonded clusters with different ring sizes in the CDC layer [18]. | [
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oastm_02 | 2+2 Gaussian profiles can be used to fit the Raman spectrum [17] to calculate the integrated intensity ratio of D- and G-bands (ID/IG ≈1.70). | [
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oastm_02 | According to the Tuinstra and Koenig (TK) equation [19,20], the in-plane correlation length (La) or the average size of the graphite sheets in the CDC layer is estimated to be about 2.92nm. | [
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oastm_02 | The Raman features of the CVD layer are similar to that of the CDC layer, although the position of D-band shifts to the higher wavenumber at ~1354cm-1. | [
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oastm_02 | Since the CVD carbon nucleates and grows on the top of CDC layer, top layer may copy the structure of CDC layer in some extent and therefore their Raman feature is similar. | [
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oastm_02 | The up-shifted D-band of CVD layer may be attributed to the increased size of the graphite microcrystalline. | [
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oastm_02 | It is also necessary to note that the densification of the CVD layer and the reduced internal stress may lead to the difference in Raman spectrum. | [
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oastm_02 | The Raman spectrum of the CVD layer was also fitted with 2+2 Gaussian mode. | [
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oastm_02 | The integrated intensity ratio (ID/IG) reduces to 1.32, corresponding to an increased La of 3.75nm compared to CDC layer. | [
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oastm_02 | XPS analysis | [
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oastm_02 | The XPS measurements were carried out aiming to determine the surface composition and chemical nature for SiC, CDC layer and dual-layer film, as demonstrated in Fig. 3. | [
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oastm_02 | It is mentioned that oxidizing of silicon carbide surface can easily take place even at room temperature [21]. | [
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Subsets and Splits