Mechanism and Modeling of Contact Damage in ZrN-Zr and TiAIN-TiN Multilayer Hard Coatings
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With the amalgamation of hard coating in cutting tools industries for three decades now, a stage with proven performance has been reached. Today, nearly 40% of all cutting tools used in machining applications are sheltered with coatings. Coatings have proven to dramatically improve wear resistance, increase tool life and enable use at higher speed. Over the years TiN, TiAlN and TiC have emerged as potential materials to coat machining tools. Chemical vapor deposition was the ﬁrst technology to be used to deposit these coatings followed by physical vapor deposition. Currently, extensive use is being made of cathodic arc evaporation and sputtering for coatings components. The principal limiting factor in the performance of these cutting tools lies in their failure due to the brittleness of these coatings. These hard coatings, usually coated on soft steel substrates, are subjected to contact damage during service. This contact damage is driven by mismatch strain between the elastically deforming ﬁlm on a plastically deforming substrate. Understanding of the contact damage is the key parameter for improvement in the coating design. Contact damage involves initiation of cracks and subsequent propagation within coating. Multiple cracking modes are seen in nitride coatings on soft substrate and mutual interaction of cracks may lead to spallation of the coating, exposing the substrate to extreme service conditions. Hence visualization of subsurface crack trajectories facilitates the classiﬁcation of benign and catastrophic modes of failure, which consequently allows us to tailor the coating architecture to eliminate catastrophic failure. Multilayers have shown to perform better then monolayer coatings. In multilayer coatings, application speciﬁc particular properties can be engineered by alternately stack-ing suitable layers. The multilayer utilizes beneﬁts of interfaces by crack deﬂection, crack blunting and desirable transition in residual stress across the interface. Hence, designing interfaces is the key parameter in the multilayer coating. However, very few studies exist that describe experimental visualization of deformation modes in multilayer coatings with diﬀerent types of interfaces, e.g. nitride/nitride and nitride/metal. Thus the prime objective of the present study is to comprehend the inﬂuence of diﬀerent interface structures as well as its architecture on the various contact damage modes in these coatings. TiAlN/TiN has shown better tribological properties compared to its constituent monolayers. There is an order of magnitude augmentation in loads for cracking without any hardness enhancement relative to monolayers of constituents, with the additional feature that both constituents exhibit similar hardness and modulus. The resistance to cracking is seen to increase with increase in number of interfaces. Hence this uniqueness in toughening without drastic reduction in mechanical properties provides the motivation for understanding the fundamental mechanisms of toughening provided by the interfaces in these hard/hard coatings. Another combination for the present study is with interfaces between hard-soft phases ZrN/Zr, a composite that seeks to compromise hardness in order to achieve greater toughness. The selected combination has potential of providing a model system without any substoichiometric nitrides inﬂuencing the interfacial structure. There is a great need to optimize the metal fraction/thickness for exploiting the beneﬁts of toughening without much compromise on hardness and stiﬀness, since the principal applications of these coatings lies in preventing erosive and corrosive wear. As all the deformation modes in theses coatings are stress driven, the inﬂuence of diﬀerent variables on stress ﬁeld would dictate the emerging damage. To understand the role of stress ﬁelds on contact damage, ﬁnite element method and an analytical model was used to predict the stress ﬁeld within the coating. The TiAlN/TiN coatings were deposited by cathodic arc evaporation, while sputtering was employed to procure the ZrN/Zr multilayer coatings with much ﬁner layer spacing. Microstructural characterization of the as received coatings was done by XRD, scanning electron microscopy, focused ion beam cross section machining and transmission electron microscopy. Mechanical properties like hardness and modulus were evaluated by nanoindentation with restricted penetration depths to allow measurements that were not inﬂuenced by the substrate. Contact damage was induced by micro indentation at high loads. Indentations were examined from plan view as well as cross section for getting details of crack nucleation as well as propagation trajectories. Focused ion beam was used to examine cross sections of indents as well as to prepare electron transparent thin foils for transmission electron microscopy examination of subsurface damage induced by indentation. To emphasize speciﬁc issues in detail, the present work is divided into four sections: 1 Microstructure and mechanical characterization of the as deposited coatings of ZrN/Zr multilayer (while that of TiAlN/TiN has been reported elsewhere) 2 Details of contact damage in ZrN/Zr coating 3 Resolution of micro mechanistic issues in TiAlN/TiN coating utilizing detailed microscopy 4 The eﬀect of change in architecture through heat-treatment of ZrN/Zr multilayer coatings on the mechanical behavior and contact damage Detailed microstructural, compositional and mechanical characterization was done on ZrN/Zr as received multilayer coatings. Thickness of metal layer was seen to inﬂuence the texture in the nitride, thick metal acquiring basal texture in turn inducing (111) texture in the nitride to reduce interfacial energy. Microstructure revealed that the nitride grows with interrupted columnar grains, renucleating at each metal/nitride interface. Presence of both phases was conﬁrmed at even very low bilayer spacing, with slight changes in multilayers architecture, from planar interfaces to curved interfaces. The chosen system proved to be an ideal system for multilayer study without formation of secondary nitrides. Residual stress and hardness reduced with increase in metal layer thickness, whereas modulus was seen to follow the rule of mixture value. Detailed contact damage study of ZrN/Zr is reported in section two with inﬂuence of volume fraction and metal layer thickness. All the experimental results were corroborated with ﬁnite element methods. A comparative study of contact damage of multilayer with monolayer was carried out with cross section as well as plan view of indents. Metal plasticity was able to distribute damage laterally as well as vertically, hence reducing the stress concentration. There lies an optimum thickness of the metal providing maximum toughening by increasing the threshold load required for edge cracking. The sliding of columns is resisted by the metal. However, thick metal layers promote microcracking in individual nitride layers. Cracking is restricted to within individual nitride layers, eliminating through thickness cracking. The intermediate metal thickness was able to provide a mechanism of laterally distributing sliding and hence a higher tolerance level of the indentation strain that can be accommodated without cracking. Thin metal multilayers were seen to show delamination, strongly inﬂuenced by the multilayer architecture. We use the ﬁnite element method to understand the inﬂuence of stress ﬁelds in driving these various modes of damage for varying volume fraction and metal layer thicknesses. It is demonstrated how metal plasticity results in stress enhancement in the nitride layer compared to a monolayer and reduces the shear stress, which is the driving force for columnar sliding. The micro cracking to columnar shearing transition with metal thickness was explained with the help of average shear and normal stress across the multilayer which could explain the transition from cracking and sliding to interfacial delamination in thin metal layer multilayers with enhancement in interfacial shear stress. TiAlN/TiN multilayer allowed to exploit a form of compositional contrast to measure the strain with respect to depth. Layers acting as strain markers quantify the amount of sliding in terms of the oﬀset in layers with respect to depth within the coating. We illustrate with transmission electron micrographs, the ﬂaw generation that occurs as a result of sliding of misaligned column boundaries. These boundary kinks,upon further loading, may lead to cracks running at an angle to the indentation axis in an otherwise dense, defect free, as deposited coating. A previous study illustrates the increase in resistance of multilayers to multiple modes of cracking that are seen in the monolayer nitride coatings on steel substrates. We provide evidence of the enhanced plasticity, seen as macroscopic bending, which in reality is column sliding in a series of distributed small steps. We discuss the role of misﬁt dislocations in spreading the material laterally to accommodate the constraints during indentation and lattice bending. Interfacial sliding is seen to reduce the stress concentration by distributing the vertical column sliding and accommodating the ﬂaws generated by the sliding of misaligned column boundaries. Some preferred boundaries with special orientation relations do slide, while near the substrate, the sliding is facilitated by the relaxation in intrinsic residual stresses. An analytical model which was formulated earlier is used to support our experimental ﬁndings. Investigations of the plausible reasons for the naturally occurring multilayer mollusc sea shells to reach stiﬀnesses equal to the upper bound of the rule of mixture value have concluded that its brick and mortar organization is responsible for its exceptional mechanical properties. Inspired by the same model, heat treatment was used to change the architecture of the soft-hard metal/nitride combination from that of the planar interface of the as deposited multilayer to a brick and mortar arrangement. Such an interconnected ZrN microstructure was successfully achieved and the stiffness and hardness were both seen to increase relative to the as received coatings. The possible reasons for this enhancement are discussed in term of this newly emerged architecture ,change in residual stress as well as changes in stoichiometry after heat treatment. The contact damage, though, was found to be more catastrophic relative to the as deposited coating with increased propensities for edge and lateral cracking. This was attributed to the interconnected nitrides formed in the brick and mortar architecture as well as residual stress changes due to the dissolution of Zr in ZrN to form oﬀ-stoichiometric nitrides. The cracks feel the presence of the metal and deviate from the otherwise smooth trajectory and take a path along the interface of the metal packet and the interconnected nitride. Summarizing, the present study clearly illustrates the fact that interfaces play an important role in damage control under contact loading. Fracture and deformation are either controlled by metal plasticity, distributing the column sliding in metal/nitride multilayers or by interfacial sliding mediated by interfacial misfit dislocations in case of the nitride/nitride multilayer coatings. The effective role of interfaces is to distribute damage laterally as well as horizontally to relieve stresses and hence enhance the damage tolerance under indentation. Optimum metal layer thickness has been proposed for maximum toughening in the metal/nitride multilayer coating and the role of interfaces in providing modes of plasticity is presented for the nitride/nitride multilayer coatings by use of extensive transmission electron microscopic investigations. A new interconnected architecture coatings provides a unique way of combining stiffness and toughness along with scope for further developing such configurations with improved mechanical properties.
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