Design, Preparation and Properties of Ti-B-N Nanocomposite Coatings
LIU Yanmei1, WANG Tiegang1(), GUO Yuyao1, KE Peiling2, MENG Deqiang1, ZHANG Jifu1
1 Tianjin Key Laboratory of High Speed Cutting and Precision Manufacturing, Tianjin University of Technology and Education, Tianjin 300222, China 2 Key Laboratory of Marine Materials and Related Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
Cite this article:
LIU Yanmei, WANG Tiegang, GUO Yuyao, KE Peiling, MENG Deqiang, ZHANG Jifu. Design, Preparation and Properties of Ti-B-N Nanocomposite Coatings. Acta Metall Sin, 2020, 56(11): 1521-1529.
TiB2 coating comprises a large number of ionic and covalent bonds, conferring it with excellent properties such as high melting point, high hardness, and good oxidation and corrosion resistances. However, its application to cutting tool surfaces is limited due to high brittleness. When doped with N atoms, TiB2 coating forms a nanocomposite structure with improved toughness. However, the hardness of the resulting coating is significantly impaired by the abundant amorphous BN (a-BN) phase. The addition of metal ions and reactive N2 increases the proportion of hard nitrides and improves the coating hardness. However, the addition of N2 increases the amount of soft a-BN phase, which largely negates the strengthening effect. To further improve the mechanical properties of Ti-B-N coating, a series of Ti-B-N coatings were prepared by pulsed direct current magnetron sputtering in this work. The content of soft-phase a-BN in the coating was reduced by decreasing the flow of reactive gas N2. Meanwhile, the amount of hard TiB2 phase was increased by increasing the sputtering power of the TiB2 target. Consequently, a noncrystalline (nc)-(Ti2N, TiB2)/a-BN nanocomposite coating with significantly improved toughness and strength was formed. The influence of TiB2 target sputtering power on the composition, microstructure, and mechanical and tribological properties of the Ti-B-N coatings were systematically investigated by EDS, TEM, SEM, XRD, and nano-indentation, scratch, and ball-on-disk tribological testings. As the sputtering power of the TiB2 target increased, the microstructure of Ti-B-N coatings gradually evolved from nc-Ti2N/a-BN to hexagonal-close-packed TiB2/a-BN, and the nanohardness also increased gradually. The particle size on the coating surface was significantly increased, and all Ti-B-N coatings were uniform and compact without pinholes and other defects. The coating with highest hardness of about 33.8 GPa was achieved under a sputtering power of 2.4 kW at the TiB2 target. This coating also exhibited the lowest friction coefficient (0.55), lowest wear rate (2.1×10-4 μm3/(N·μm)), and best wear resistance.
Fund: National Natural Science Foundation of China(51301181);National Natural Science Foundation of China(51875555);Tianjin Science and Technology Major Project(18ZXJMTG00050);Tianjin Natural Science Foundation(19JCYBJC17100)
Table 1 Deposition parameters of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
Fig.1 Chemical compositions of the Ti-B-N coating prepared by different sputtering powers of the TiB2 target
Fig.2 XRD spectra of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
Fig.3 Cross-sectional (a~e) and surface (f~j) SEM images of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target (a, f) 0.8 kW (b, g) 1.2 kW (c, h) 1.6 kW (d, i) 2.0 kW (e, j) 2.4 kW
Fig.4 HRTEM image and SAED pattern (inset) for the Ti-B-N coating prepared under a sputtering power of 2.4 kW at the TiB2 target (The zones marked with ellipse represent the TiB2 nanocrystals)
Fig.5 Deposition rates of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
Fig.6 Nanohardnesses of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
Fig.7 Critical loads of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
Fig.8 Average friction coefficients of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
Fig.9 OM images of worn scar of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target (a) 0.8 kW (b) 1.2 kW (c) 1.6 kW (d) 2.0 kW (e) 2.4 kW
Fig.10 Wear rates of the Ti-B-N coatings prepared by different sputtering powers of the TiB2 target
[1]
Panich N, Sun Y. Effect of substrate rotation on structure, hardness and adhesion of magnetron sputtered TiB2 coating on high speed steel [J]. Thin Solid Films, 2006, 500: 190
[2]
Ott R D, Ruby C, Huang F, et al. Nanotribology and surface chemistry of reactively sputtered Ti-B-N hard coatings [J]. Thin Solid Films, 2000, 377-378: 602
[3]
Panich N, Sun Y. Mechanical characterization of nanostructured TiB2 coatings using microscratch techniques [J]. Tribol. Int., 2006, 39: 138
[4]
Lin Y H, Yao J H, Lei Y P, et al. Microstructure and properties of TiB2-TiB reinforced titanium matrix composite coating by laser cladding [J]. Opt. Lasers Eng., 2016, 86: 216
[5]
Berger M, Hogmark S. Evaluation of TiB2 coatings in sliding contact against aluminium [J]. Surf. Coat. Technol., 2002, 149: 14
[6]
Sanchez C M T, Plata B R, da Costa M E H M, et al. Titanium diboride thin films produced by dc-magnetron sputtering: Structural and mechanical properties [J]. Surf. Coat. Technol., 2011, 205: 3698
[7]
Wang X, Martin P J, Kinder T J. Characteristics of TiB2 films prepared by ion beam sputtering [J]. Surf. Coat. Technol., 1996, 78: 37
[8]
Shi J, Kumar A, Zhang L, et al. Effect of Cu addition on properties of Ti-Al-Si-N nanocomposite films deposited by cathodic vacuum arc ion plating [J]. Surf. Coat. Technol., 2012, 206: 2947
[9]
Liu Y M, Deng D Y, Lei H, et al. Effect of nitrogen content on microstructures and mechanical properties of WB2(N) films deposited by reactive magnetron sputtering [J]. J. Mater. Sci. Technol., 2015, 31: 1217
[10]
Mayrhofer P H, Stoiber M. Thermal stability of superhard Ti-B-N coatings [J]. Surf. Coat. Technol., 2007, 201: 6148
[11]
Veprek S, Veprek-Heijman M G J. Limits to the preparation of superhard nanocomposites: Impurities, deposition and annealing temperature [J]. Thin Solid Films, 2012, 522: 274
[12]
Neidhardt J, O'Sullivan M, Reiter A E, et al. Structure-property-performance relations of high-rate reactive arc-evaporated Ti-B-N nanocomposite coatings [J]. Surf. Coat. Technol., 2006, 201: 2553
[13]
Wang T G, Guo Y Y, Tang K Y, et al. Influence of nitrogen flow on structure and performance of the Zr-B-N films prepared by hybrid magnetron sputtering techniques [J]. Surf. Technol., 2018, 47(11): 210
Yu L H, Zhao Q, Ma B Y, et al. Effect of B target power on microstructure, mechanical properties and friction properties of ZrBN composite films [J]. Mater. Sci. Eng. Powder Metall., 2013, 18: 748
Kang M S, Wang T G, Kim K H, et al. Synthesis and properties of Cr-Al-Si-N films deposited by hybrid coating system with high power impulse magnetron sputtering (HIPIMS) and DC pulse sputtering [J]. Trans. Nonferrous Met. Soc. China, 2012, 22(S3): S729
[17]
Wang T G, Liu Y M, Zhang T F, et al. Influence of nitrogen flow ratio on the microstructure, composition, and mechanical properties of DC magnetron sputtered Zr-B-O-N films [J]. J. Mater. Sci. Technol., 2012, 28: 981
[18]
Mitterer C, Mayrhofer P H, Beschliesser M, et al. Microstructure and properties of nanocomposite Ti-B-N and Ti-B-C coatings [J]. Surf. Coat. Technol., 1999, 120-121: 405
[19]
Pfohl C, Rie K T. Wear-resistant PACVD coatings of the system Ti-B-N [J]. Surf. Coat. Technol., 1999, 116-119: 911
doi: 10.1016/S0257-8972(99)00141-3
[20]
Shin J H, Choi K S, Wang T G, et al. Microstructure evolution and mechanical properties of Ti-B-N coatings deposited by plasma-enhanced chemical vapor deposition [J]. Trans. Nonferrous Met. Soc. China, 2012, 22(S3): S722
[21]
Li C, Dong L, Yu J G, et al. Influence of sputtering power on structure and mechanical properties of Zr-B-Nb-N nanocomposite films [J]. J. Tianjin Normal Univ. (Nat. Sci. Ed.), 2016, 36(6): 13
Kunc F, Musil J, Mayrhofer P H, et al. Low-stress superhard Ti-B films prepared by magnetron sputtering [J]. Surf. Coat. Technol., 2003, 174-175: 744
[23]
Lin J L, Moore J J, Mishra B, et al. The structure and mechanical and tribological properties of TiBCN nanocomposite coatings [J]. Acta Mater., 2010, 58: 1554
[24]
Samuelsson M, Jensen J, Helmersson U, et al. ZrB2 thin films grown by high power impulse magnetron sputtering from a compound target [J]. Thin Solid Films, 2012, 526: 163
[25]
Lu C Y, Diyatmika W, Lou B S, et al. Influences of target poisoning on the mechanical properties of TiCrBN thin films grown by a superimposed high power impulse and medium-frequency magnetron sputtering [J]. Surf. Coat. Technol., 2017, 332: 86
[26]
Ding J C, Zhang T F, Yun J M, et al. Effect of Cu addition on the microstructure and properties of TiB2 films deposited by a hybrid system combining high power impulse magnetron sputtering and pulsed dc magnetron sputtering [J]. Surf. Coat. Technol., 2018, 344: 441
[27]
Fager H, Greczynski G, Jensen J, et al. Growth and properties of amorphous Ti-B-Si-N thin films deposited by hybrid HIPIMS/DC-magnetron co-sputtering from TiB2 and Si targets [J]. Surf. Coat. Technol., 2014, 259: 442
[28]
Depla D, De Gryse R. Target poisoning during reactive magnetron sputtering: Part III: The prediction of the critical reactive gas mole fraction [J]. Surf. Coat. Technol., 2004, 183: 196
[29]
Wang T G, Zhao S S, Hua W G, et al. Design of a separation device used in detonation gun spraying system and its effects on the performance of WC-Co coatings [J]. Surf. Coat. Technol., 2009, 203: 1637
doi: 10.1016/j.surfcoat.2008.12.012
[30]
Wang Z Y, Xu S, Zhang D, et al. Influence of N2 flow rate on structures and mechanical properties of TiSiN coatings prepared by hipims method [J]. Acta Metall. Sin., 2014, 50: 540
doi: 10.3724/SP.J.1037.2013.00698
Burnett D J, Rickerby D S. The relationship between hardness and scratch adhession [J]. Thin Solid Films, 1987, 154: 403
doi: 10.1016/0040-6090(87)90382-8
[32]
Rossi S, Fedrizzi L, Leoni M, et al. (Ti, Cr)N and Ti/TiN PVD coatings on 304 stainless steel substrates: Wear-corrosion behaviour [J]. Thin Solid Films, 1999, 350: 161
doi: 10.1016/S0040-6090(99)00235-7
[33]
Panich N, Sun Y. Mechanical properties of TiB2-based nanostructured coatings [J]. Surf. Coat. Technol., 2005, 198: 14
doi: 10.1016/j.surfcoat.2004.10.096
[34]
Wang T G, Meng D Q, Li B S, et al. Preparation and tribological properties of Cr-Al-Si-N nanocomposite coatings by three target co-sputtering [J]. Surf. Technol., 2019, 48(9): 78
Liu Y M, Han R Q, Liu F, et al. Sputtering gas pressure and target power dependence on the microstructure and properties of DC-magnetron sputtered AlB2-type WB2 films [J]. J. Alloys Compd., 2017, 703: 188
doi: 10.1016/j.jallcom.2017.01.337
[37]
Wang T G, Zhao S S, Hua W G, et al. Design of a separation device used in detonation gun spraying system and its effects on the performance of WC-Co coatings [J]. Surf. Coat. Technol., 2009, 203: 1637
doi: 10.1016/j.surfcoat.2008.12.012
[38]
Kuo Y C, Wang C J, Lee J W. The microstructure and mechanical properties evaluation of CrTiAlSiN coatings: Effects of silicon content [J]. Thin Solid Films, 2017, 638: 220
[39]
Hou X, Wang T G, Liu Y, et al. Deposition technology of TiN coatings prepared by arc ion plating [J]. Equip. Environ. Eng., 2019, 16(5): 72
Zheng Y J, Leng Y X, Xin X, et al. Evaluation of mechanical properties of Ti(Cr)SiC(O)N coated cemented carbide tools [J]. Vacuum, 2013, 90: 50
[41]
Wang T G, Dawoon J, Liu Y M, et al. Study on nanocrystalline Cr2O3 films deposited by arc ion plating: II. Mechanical and tribological properties [J]. Surf. Coat. Technol., 2012, 206: 2638
