Structure and tribological properties of TiSiCN coating on Ti6Al4V by arc ion plating

Structure and tribological properties of TiSiCN coating on Ti6Al4V by arc ion plating

    Structure and tribological properties of TiSiCN coating on Ti6Al4V by arc ion plating Jinlong Li, Yue Wang, Yirong Yao, Yongxin Wang,...

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    Structure and tribological properties of TiSiCN coating on Ti6Al4V by arc ion plating Jinlong Li, Yue Wang, Yirong Yao, Yongxin Wang, Liping Wang PII: DOI: Reference:

S0040-6090(17)30736-8 doi:10.1016/j.tsf.2017.09.053 TSF 36261

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Thin Solid Films

Received date: Revised date: Accepted date:

21 March 2017 4 September 2017 6 September 2017

Please cite this article as: Jinlong Li, Yue Wang, Yirong Yao, Yongxin Wang, Liping Wang, Structure and tribological properties of TiSiCN coating on Ti6Al4V by arc ion plating, Thin Solid Films (2017), doi:10.1016/j.tsf.2017.09.053

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ACCEPTED MANUSCRIPT Structure and tribological properties of TiSiCN coating on Ti6Al4V by arc ion plating Jinlong Li, Yue Wang, Yirong Yao, Yongxin Wang, Liping Wang

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Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of

PR China

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Abstract

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Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201,

The TiSiCN coating was fabricated on Ti6Al4V alloy by arc ion plating.

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The structure of the TiSiCN coating was characterized using Scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy

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and Transmission electron microscopy. The hardness and tribological properties of the TiSiCN coating were evaluated by nanoindentation and

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ball-on-plate wear tests. The coating has a coupled structure of the TiCN nanocrystal and amorphous phase (Si3N4 and SiC). The TiSiCN coating has

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a super high hardness of 43.6 GPa and modulus of 422 GPa. The values of H/E and H3/E2 are 0.103 to 0.465, respectively. The coating has a low friction coefficient of 0.3, and the wear loss is 1.76 × 10-6 mm3/Nm, which is only 1/3 of wear loss of the TiSiN coating. The TiCN phase contributes to significantly decrease of the friction coefficient and wear rate for the TiSiCN coating. Keywords: TiSiCN coatings; Arc ion plating; Structure; Hardness, Tribological behavior

ACCEPTED MANUSCRIPT 1. Introduction Titanium alloy were widely used in aerospace, medicine, submersibles,

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and marine equipment as the key components due to its high specific

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strength, particularly excellent corrosion resistant in marine environment [1,

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2]. However, the titanium alloy has a poor wear resistance, thus the surface treatment is necessary before application in many applications.

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The hard coating protection is a promising method to improve the wear resistance of the titanium alloy by physical vapor deposition (PVD). The

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TiN coating was incorporated with Si to form the TiSiN coating, which has

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higher hardness due to the coupled structure of the nanocrystal-TiN and

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amorphous-Si3N4[3, 4]. Veprek et al. have reported a TiSiN coating with super hardness about 50-60 GPa [5]. PVD technique is considered more

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suitable to synthesis the TiSiN coatings [6-7]. Many researchers have reported the hardness enhancement mechanism, thermal stability and

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tribological behavior of the TiSiN coatings [8-10]. The TiSiN coating has a super high hardness, but its friction coefficient is very high, thus its wear resistance is not perfect. In recent years, some researchers have tried to fabricate TiSiCN coatings. The carbon is incorporated into TiSiN coating and can form a TiC phase. For the TiSiCN coating, the coupled structure of TiCN and amorphous-nanocrystalline can achieve balance property of the lubrication and high hardness, and it is promising method to improve the wear resistance greatly for titanium alloy. Some researcher’s works have reported the structure and properties of the

ACCEPTED MANUSCRIPT TiSiCN coating [12-14]. D.Y. Ma et al. [12] investigated that the effects of the concentration of C and Si on the tribological properties of TiSiCN

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coatings fabricated by plasma enhanced chemical vapor deposition at room

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temperature and elevated temperature, respectively. The TiSiCN coating

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that deposited at higher power densities exhibited excellent corrosion resistance had been reported [13].

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In this study, the TiSiCN coatings were synthesized on the Ti6Al4V substrate using arc ion plating technique. The structure and tribological

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properties of the TiSiCN coatings were investigated systematically.

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2. Experimental

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The TiSiCN coatings were deposited using arc ion plating with the TiSi targets (90 at.% Ti, 10 at.% Si; purity 99.99 at.%) in C2H2/N2/argon gas

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atmosphere. The Ti6Al4V substrates were grounded and polished to the mirror, then ultrasonically cleaned in acetone for 5 minutes, respectively.

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The chamber was pumped down to a background pressure below 4 × 10 -3 Pa, then the substrates were cleaned by etch cleaning with negative bias voltages of 900 V, 1100 V and 1200 V, respectively. For the deposition of TiSiCN coatings, N2, C2H2 and argon gas with the flow rate of 420 sccm, 60 sccm, and 470 sccm were introduced to chamber, and the work pressure was maintained at 0.3 Pa. The target current was 65 A and the negative bias was 100 V. The deposition temperature is 500 ºC. After deposition, the annealing at 700 ºC also was performed to obtain more MAX phase. The cross-sectional images of the coatings were obtained using a field

ACCEPTED MANUSCRIPT emission scanning electron microscope (Hitachi S4800). The crystal structure of the coatings were characterized by X-ray diffraction with a

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type of Bruker D8 using Kα radiation (λ = 0.154 nm) operated at 40 kV and

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scanning speed of 4°/min with 0.02° step size. X-ray photoelectron

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spectroscopy (XPS) (Kratos Axis UltraDLD) using an Al Kα X-ray source was used to investigate the element chemical state. The structure of TiSiCN

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coatings were observed by high resolution transmission electron microscopy in a FEI Tecnai F20. The hardness and elastic modulus were

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performed on a nanoindenter (MTS G200) with a Berkovich diamond

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indenter and using the continuous stiffness measurement (CSM) mode. The

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wear tests were performed by a reciprocating ball-on-plate. In the test, WC ball with a diameter of 6 mm were used as sliding counterface and applied

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normal load of 5 N. The images of wear track of the TiSiCN coatings were observed by field emission scanning electron microscope (FEI Quanta FEG

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250) equipped with EDS (OXFORD X-Max). The depth profiles of wear tracks and the roughness of the coatings were examined using a surface profilometer (Alpha-Step IQ) by taking average measurements along the wear track. 3. Results and discussion 3.1 Morphologies and structure Figure 1 shows the surface and cross-section SEM images of the TiSiCN coatings. It is found that many droplets embedded in the coatings, which is the feature of the coating deposited by ion plating. The TiSiCN coating has

ACCEPTED MANUSCRIPT a slightly columnar structure with a thickness of 2.2 m. The element chemical states of the TiSiCN coatings were characterized

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by XPS. The core levels spectra of Ti2p, Si2p, C1s and N1s are shown in

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Figure 2. The argon sputtering was employed to remove the surface

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contamination layer for 5 min before measurement. The fitted Ti 2p spectrum reveals that the peaks of 454.8 eV /460.5 eV and 456.0 eV /462.0

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eV are correspond to TiC and TiN respectively [15]. Additionally, the peaks at 457.5 eV /463.5 eV and 459 eV /464.8 eV are presented as Ti2O3 and

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TiO2, respectively [16]. The Si 2p spectra are composed of two peaks of

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Si-N (101.4 eV) and Si-C (100.2 eV) [17, 18]. The C 1s spectra are

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deconvoluted as four peaks positioned at 281.8 eV, 282.8 eV, 285 eV and 286.4 eV, which were attributed to C–Ti, C-Si, C-C and C-N bonds [19, 20].

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The N 1s spectrum of the as-deposited coatings could be fitted as three peaks at 396.1 eV, 398.1 eV and 399.9 eV, attributed to Ti-N, Si-N and N-C

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bonds [6], respectively.

Figure 3 shows the XRD pattern from the TiSiCN coatings. The diffraction peaks of TiCN (111), TiCN (200) and TiCN (220) were detected from the XRD pattern. The FWHM of these peaks is very large and this implies the TiCN crystals are very small. The diffraction peaks of Ti6Al4V substrate also were found, because the as deposited TiSiCN coatings are not very thick, thus the information from substrate can be detected. Figure 4 shows the High resolution TEM images of the TiSiCN coatings. It is clear that the coupled structure of the nanocrystal TiCN embedded in the

ACCEPTED MANUSCRIPT amorphous matrix. The size of the nanocrystal TiCN is about several nanometers, and this is in good agreement with the XRD results. The Moire

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pattern structure is found near to nanocrystal TiCN. The XPS core spectra

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reveal Si3N4 and SiC exist in the TiSiCN coating, but the X-ray diffraction

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pattern and TEM image do not found the corresponding information of Si3N4 and SiC, and this implies that Si exists as amorphous phases of Si3N4

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and SiC in the TiSiCN coatings. 3.2 Hardness

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The variation of the hardness with displacement into surface is shown in

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Figure 5 for the TiSiCN coatings and TiSiN coating as reference sample.

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The hardness of the TiSiCN coating can be identified in the platform area at the near surface, and its hardness reaches 43.6 GPa and the modulus is 422

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GPa. With increasing displacement into surface, the hardness decreases due to the effect from the soft substrate. However, the hardness and modulus of

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the TiSiN coating are 37 GPa and 640 GPa, respectively. The TiSiCN coating has super high hardness and the reason is that the coating has two species nanocrystals of TiN and TiC, thus the grain size is very small and leads to the super high hardness. The H/E and H3/E2 is important mechanical indexes and it is convenient to evaluate the ability of resistance elastic strain to failure of the coating. In general, the coating has high hardness, low elastic modulus and residual compressive stress, and this implies that the coating has excellent delaying failure and resistance to crack formation. The values of H/E and H3/E2 of

ACCEPTED MANUSCRIPT the TiSiN coatings are 0.056 to 0.116, respectively. The values of H/E and H3/E2 of the TiSiCN coatings are 0.103 to 0.465, respectively. It is clear

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that the TiSiCN coating has a high value of H/E and H3/E2 and this implies

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that the coating has excellent ability of resistance elastic strain to failure.

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3.3 Tribological behavior

Figure 6 shows the friction coefficients for the TiSiCN and TiSiN coatings.

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The TiSiCN coating has a low friction coefficient of about 0.3, which is far lower than 0.5 for TiSiN coating. This may be ascribed to the TiCN phase

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which can be acts as solid lubricating in the TiSiCN coating. Figure 7

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shows the wear loss of the TiSiCN and TiSiN coatings. The wear loss was

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calculated by the formula K=V/FS, where the V is the volume of the wear loss of coating, S is the total sliding distance and F is the normal load

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applied. The TiSiCN coating has a low wear loss of 1.76 × 10-6 mm3/Nm, which is only 1/3 of wear loss of the TiSiN coating. Such lower wear loss is

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contributed to the super high hardness and low friction coefficient of the TiSiCN coating. Figure 8 shows the SEM images and EDS composition analysis on the wear tracks of the TiSiCN and TiSiN coatings. It is clear that the wear tracks of the TiSiCN coating is uniform and very smooth, but the wear track surface of the TiSiN coating is not smooth and shows a furrows images parallel to the sliding direction for the typical abrasive wear. By the EDS composition analysis on the wear track, Ti, Si, C, O and W were found. The W is transformed from the friction pair of the WC ball. The TiCN phase and titanium oxides play a lubricating role during wear

ACCEPTED MANUSCRIPT test, thus the track surface is very smooth for the TiSiCN coating. 4. Conclusion

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The TiSiCN coating was fabricated on Ti6Al4V alloy using arc ion plating

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and subsequent annealing. The coating has a coupled structure of the TiCN

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nanocrystal and amorphous phase (Si3N4 and SiC). The TiSiCN coating has super high hardness of 51 GPa and the modulus of 548 GPa. The values of

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H/E and H3/E2 of the TiSiCN coatings are 0.103 to 0.465, respectively. The TiSiCN coating has a low friction coefficient of 0.3, and the wear loss is

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1.76 × 10-6 mm3/Nm, which is only 1/3 of wear loss of the TiSiN coating.

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Acknowledgements

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This work has been supported by the National Key Research and Development Program of China (Grant No. 2016YFB0300604) and

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National Natural Science Foundation of China (Grant No. 51575510).

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ACCEPTED MANUSCRIPT List of Figure Captions Figure 1 Surface and cross-section SEM images of TiSiCN coatings

coating

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Figure 3 XRD pattern from TiSiCN coating

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Figure 2 Core levels spectra of Ti2p, Si2p, C1s and N1s from TiSiCN

Figure 4 High resolution TEM images of TiSiCN coating

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Figure 5Variation of hardness with displacement into surface from TiSiCN and TiSiN coatings

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Figure 6 Friction coefficients from TiSiCN and TiSiN coatings against WC

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ball.

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Figure 7 Wear loss of TiSiCN and TiSiN coatings Figure 8 SEM images and EDS composition analysis on wear tracks of

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TiSiCN and TiSiN coatings.

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Ti(C,N) Substrate

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Figure 3

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Moire pattern

TiCN (200) d=2.15 Å

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TiSiCN

Element

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Ti(at.%)

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O(at.%)

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C(at.%)

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Si(at.%)

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W(at.%)

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TiSiN

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ACCEPTED MANUSCRIPT Highlights The TiSiCN coatings were deposited on Ti6Al4V alloy by arc ion plating.



The coupled structure of nanocrystal and amorphous was fabricated.



The coatings have a super high hardness of 43.6 GPa and low friction coefficient.



The TiCN phase contributes to significant improvement of wear resistance.

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