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Phase, microstructure, and strain evolution during annealing of arc deposited TiZrAlN coatings are studied using in situ x-ray scattering and ex situ transmission electron microscopy. We find that the decomposition route changes from nucleation and growth of wurtzite AlN to spinodal decomposition when the Zr-content is decreased and the Al-content increases. Decomposition of Ti0.31Zr0.24Al0.45N results in homogeneously distributed wurtzite AlN grains in a cubic, dislocation-dense matrix of TiZrN consisting of domains of different chemical composition. The combination of high dislocation density, variation of chemical composition within the cubic grains, and evenly distributed wurtzite AlN grains results in high compressive strains, -1.1%, which are retained after 3 h at 1100 degrees C. In coatings with higher Zr-content, the strains relax during annealing above 900 degrees C due to grain growth and defect annihilation. (C) 2018 Elsevier B.V. All rights reserved. Funding Agencies|VINNOVA (Swedish Governmental Agency for Innovation Systems) [2016-05156]; Swedish Government Strategic Research Area (SFO Mat LiU) [2009 00971]; Swedish Research Council [2017-03813]; Rontgen-Angstrom Cluster frame grants [VR 2011-6505, VR 2017-06701]

Nitrogen deficient c-(Ti0.52Al0.48)Ny, y = 0.92, y = 0.87, and y = 0.75 coatings were prepared in different N2/Ar discharges on WC-Co inserts by reactive cathodic arc deposition. The microstructure of the y = 0.92 coating show that spinodal decomposition has occurred resulting in the formation of coherent c-TiN- and c-AlN rich domains during cutting. The y = 0.87 and y = 0.75 coatings have exhibited a delay in decomposition due to the presence of nitrogen vacancies that lowers the free energy of the system. In the decomposed structure, grain boundaries and misfit dislocations enhance the diffusion of elements from the workpiece and the substrate (e.g. Fe, Cr, and Co) into the coatings and it becomes more susceptible to crater wear. The y = 0.87 sample displays the highest crater wear resistance because of its dense grain boundaries that prevent chemical wear. The y = 0.92 sample has the best flank wear resistance because the decomposition results in age hardening. The y = 0.75 sample contains the MAX-phase Ti2AlN after cutting. The chemical alteration within the y = 0.75 sample and its high amount of macroparticles cause its low wear resistance. The different microstructure evolution caused by different amount of N-vacancies result in distinctive interactions between chip and coating, which also causes difference in the initial wear mechanism of the (Ti,Al)Ny coatings.

The effect of varying nitrogen vacancies on the growth, microstructure, spinodal decomposition and hardness values of predominantly single crystal cubic phase c-(Ti1-xAlx)N-y films was investigated. Epitaxial c-(Ti1-xAlx)N-y films with y = 0.67, 0.79, and 0.92 were grown on MgO(001) and MgO(111) substrates by magnetron sputter deposition. High N vacancy c-(Ti1-xAlx)N-0.67 films deposited on MgO(111) contained coherently oriented w-(0001) structures while segregated conical structures were observed on the films grown on MgO(001). High resolution STEM images revealed that the N-deficient growth conditions induced segregation with small compositional fluctuations that increase with the number of N vacancies. Similarly, strain map analysis of the epitaxial c-(Ti1-xAlx)N-y (001) and (111) films show fluctuations in strain concentration that scales with the number of N vacancies and increases during annealing. The spinodal decomposition coarsening rate of the epitaxial c-(Ti1-xAlx)N-y films was observed to increase with decreasing N vacancies. Nanoindentation showed decreasing trends in hardness of the as-deposited films as the N vacancies increase. Isothermal post-anneal at 1100 degrees C in vacuum for 120 min revealed a continuation in the increase in hardness for the film with the largest number of N vacancies (y = 0.67) while the hardness decreased for the films with y = 0.79 and 0.92. These results suggest that nitrogen-deficient depositions of c-(Ti1-xAlx)N-y films help to promote a self-organized phase segregation, while higher N vacancies generally increase the coherency strain which delays the coarsening process and can influence the hardness at high temperatures. (C) 2020 Acta Materialia Inc. Published by Elsevier Ltd. Funding Agencies|European Unions Erasmus Mundus doctoral program in Materials Science and Engineering (DocMASE)European Union (EU); Swedish Research CouncilSwedish Research Council [2017-03813, 2017-06701]; Swedish government strategic research area grant AFM - SFO MatLiU [2009-00971]; VINNOVA (FunMat-II project)Vinnova [2016-05156]

Journal of alloys and compounds 854, 157205 (2021). doi:10.1016/j.jallcom.2020.157205, studied as a function of isothermal annealing. Two compositionally similar but structurally differentcoatings were compared, a Ti$_{0.34}$Al$_{0.66}$N$_{0.96}$ coating with a fine-grain structure consisting of a mixture ofcubic (c) and hexagonal (h) phases, and a Ti$_{0.40}$Al$_{0.60}$N$_{0.94}$ coating with a coarse-grain structure of cubicphase. By in situ wide-angle synchrotron x-ray scattering, spinodal decomposition was confirmed in bothcoatings. The increased amount of internal interfaces lowered the decomposition temperature by 50 Cfor the dual-phase coating. During the subsequent isothermal anneal at 1000 C, a transformation from c-AlN to h-AlN took place in both coatings. After 50 min of isothermal annealing, atom probe tomographydetected small amounts of Al (~2 at.%) in the c-TiN rich domains and small amounts of Ti (~1 at.%) in theh-AlN rich domains of the coarse-grained single-phase Ti$_{0.40}$Al$_{0.60}$N$_{0.94}$ coating. Similarly, at the sameconditions, the fine-grained dual-phase Ti$_{0.34}$Al$_{0.66}$N$_{0.96}$ coating exhibits a higher Al content (~5 at.%) inthe c-TiN rich domains and higher Ti content (~15 at.%) in the h-AlN rich domains. The study shows thatthe thermal stability of TiAlN is affected by the microstructure and that it can be used to tune the reactionpathway of decomposition favorably., Published by Elsevier, Lausanne

In view of the increasing demand for achieving sustainable development, the quest for lowering energy consumption during thin film growth by magnetron sputtering becomes of particular importance. In addition, there is a demand for low-temperature growth of dense, hard coatings for protecting temperature-sensitive substrates. Here, we explore a method, in which thermally-driven adatom mobility, necessary to obtain high-quality fully-dense films, is replaced with that supplied by effective low-energy recoil creation resulting from high-mass metal ion irradiation of the growing film surface. This approach allows the growth of dense and hard films with no external heating at substrate temperatures T-s not exceeding 130 degrees C in a hybrid high-power impulse and de magnetron co-sputtering (HiPIMS/DCMS) setup involving a high mass (m > 180 amu) HiPIMS target and metal- ion-synchronized bias pulses. We specifically investigate the effect of the metal ion mass on the extent of densification, phase content, nanostructure, and mechanical properties of metastable cubic Ti0.50Al0.50N based thin films, which present outstanding challenges for phase stability control. Ti0.50Al0.50N based thin films are irradiated by group VIB transition metal (TM) target ions generated by Me-HiPIMS discharge, in which Me = Cr (m(Cr)= 52.0 amu), Mo (m(Mo) = 96.0 amu), and W (m(W) = 183.8 amu). Three series of (Ti1-yAly)(1-x)MexN films are grown with x = Me/(Me+Al+Ti) varied intentionally by adjusting the DCMS powers, while y = Al/(Al+Ti) also varies as a result of Me+ ion irradiation. Results reveal a strong dependence of film properties on the mass of the HiPIMS-generated metal ions. All layers deposited with Cr+ irradiation exhibit porous nanostructure, high ox- ygen content, and poor mechanical properties. In contrast, (Ti1-yAly)(1-x)WxN films are fully-dense even with the lowest W concentration, x = 0.09, show no evidence of hexagonal AlN precipitation, and exhibit state-of the-art mechanical properties typical of Ti0.50Al0.50N grown at 500 degrees C. The process energy consumption is lowered by 64% with no negative impact on the coating quality. TRIM simulations provide an insight into the densification mechanisms. Funding Agencies|Swedish Energy AgencySwedish Energy Agency [51201-1]; Knut and Alice Wallenberg Foundation Scholar Grant [KAW2016.0358]; Competence Center Functional Nanoscale Materials (FunMat-II) VINNOVA grantVinnova [201605156]; Swedish Research Council VR Grant [2018-03957]; VINNOVA grantVinnova [2019-04882]; Carl Tryggers Stiftelse for Vetenskaplig Forskning [CTS 17:166, CTS 15:219, CTS 14:431]; Swedish Research Council VR-RFISwedish Research Council [2017-00646_9]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RIF14-0053]

Hybrid high power impulse/direct current magnetron sputtering (HiPIMS/DCMS) film growth technique with metal-ion-synchronized substrate bias allows for significant energy savings as compared to conventional PVD methods. For carefully selected type of metal ion irradiation, taking into account ion mass, ionization potential, and reactivity towards working gas, fully dense and hard films can be obtained with no intentional substrate heating. The thermally-driven adatom mobility, which is an essential densification mechanism in conventional film growth that takes place at elevated temperatures, is replaced with that supplied by effective low-energy recoil creation. In this contribution we explore effects of the high-mass W+ irradiation, which has proven to be the most efficient in densifying Ti0.50Al0.50N layers, serving here as a model system, grown with no substrate heating. We study the effects of two essential parameters: W+ energy EW+ and W concentration x, on film porosity, phase content, nanostructure, and mechanical properties. EW+ varies from similar to 90 to similar to 630 eV (controlled by substrate bias voltage amplitude V-s) and x from 0.02 to 0.12 (controlled by the HiPIMS pulse length), while the HiPIMS peak target current is kept constant. Results reveal that a strong coupling exists between the W+ incident energy and the minimum W concentration required to grow dense layers. Funding Agencies|Swedish Research Council VRSwedish Research Council [2018-03957]; Swedish Energy AgencySwedish Energy Agency [51201-1]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW2016.0358]; Competence Center Functional Nanoscale Materials (FunMat-II) VINNOVA grantVinnova [2016-05156]; Carl Tryggers Stiftelse for Vetenskaplig Forskning [CTS 20:150, CTS 15:219, CTS 14:431]; Swedish research council VR-RFISwedish Research Council [2017-00646_9]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RIF14-0053]

The influence of the aluminium content (x) on crater wear mechanisms of Ti1-xAlxN coated WC-Co inserts in highspeed turning of 316L stainless steel was investigated. Electron microscopy and energy dispersive X-ray spectroscopy were used to characterize the wear behaviour. Ti1-xAlxN coatings with x Funding Agencies|VINNOVAVinnova [2016-05156]; Swedish government strategic research area grant AFM -SFO MatLiU [2009-00971]

WC-Co cemented carbides (hardmetals) represent the backbone materials for the tooling industry. In order to achieve particular tool geometries, diamond wheel grinding is a well-established method for machining hardmetals. Grinding-induced damage has been proven to strongly affect the performance and reliability of the machined tools. Assessment of grinding-mechanisms and induced surface integrity changes has usually been limited to monolithic ceramics, and it is particularly done on the basis of post-failure fractographic examination. In this work, characterization of grinding-induced damage of a WC-Co grade has been conducted by means of focused ion beam (FIB) tomography. The study includes a 3D description of the damage scenario, based on a reconstruction from successive parallel slices. Our results show that grinding induces a 200-400 nm thick surface layer containing fragmented WC grains and smeared Co phase morphology. A highly anisotropic subsurface microcrack network is generated. The discerned microcracks follow different microstructural paths: running through the binder, close to WC/Co interfaces or transgranular within the carbide phase. Very interesting, completely or near- lateral cracks (parallel to the ground surface) are found to be the predominant damage feature, whereas only few completely or near- orthogonal (perpendicular to the ground surface) cracks are discerned. Results are discussed in terms of material removal mechanisms during grinding of cemented carbides and surface integrity effects on the mechanical performance of hardmetal tools under service conditions.

Using first principles calculations and experimental methods we show that B1 structured solid solution TixNbyAlzN can be grown. The mixing free energy surface indicates that the alloys should decompose. Theoretical analysis of the thermodynamic driving force towards the spinodal decomposition shows that the force can be different in alloys with equally low thermodynamic stability but different Nb content, indicating that the detailed picture of the decomposition should also be different. Electron microscopy and nanoindentation underlines different age hardening of the samples. We demonstrate that an alloy with the optimized composition, Ti0.42Nb0.17Al0.41N combines high thermal stability and age hardening behavior. Keywords: Hard coating films, NbN, Cathodic arc deposition, Thermodynamic stability, Hardness

The metallic binder phase dictates the toughening behavior of WC-Co cemented carbides (hardmetals), even though it occupies a relative small fraction of the composite. Studies on deformation and phase transformation of the binder constituent are scarce. Grinding represents a key manufacturing step in machining of hardmetal tools, and is well-recognized to induce surface integrity alterations. In this work, metallurgical alterations of the binder phase in ground WC-Co cemented carbides have been assessed by a combination of electron back scattered diffraction and transmission electron microscopy techniques. The Co-base binder experiences a martensitic phase transformation from fcc to hcp crystal structure, predominantly in the first 5 µm below the surface. The hcp fraction decreases gradually along a depth of 10 µm. Surface Co displays severe plastic deformation under the highest strain, resulting in formation of nanocrystalline grains in the first micrometer below the surface. Microstructural refinement within the binder phase is observed even at greater depth. Stacking faults were detected in most of the refined grains. The metallurgical alterations of the binder phase modify the local stress distribution during grinding, which affects the discerned subsurface microcracking. The resulting residual stress profile is the sum of multiple subsurface changes, such as phase transformation, severe plastic deformation and grain refinement, where it is discerned that the depth profile of the transformed hcp-Co fraction coincides with the grinding-induced residual stress profile.

Nitrogen sub-stoichiometric (Ti0.52Al0.48)Ny (0.92 ≥ y ≥ 0.46) coatings were grown in a mixed Ar/N2 atmosphere by cathodic arc deposition on cemented carbide (WC/Co-based) substrates. The coatings ...

We have explored the high entropy alloy (HEA) concept in the AlTiVNbCr-nitride material system. (AlTiVNbCr)N coatings synthesized by reactive cathodic arc deposition are close to an ideal cubic solid solution with a positive mean-field enthalpy of mixing of 0.06 eV/atom. First principle calculations show a higher thermodynamic stability for the solid solution relative to their binaries thereby indicating a possible entropy stabilization at a temperature above 727 °C. However, the elevated temperature annealing experiments show that the solid solution decomposes to w-AlN and c-(TiVNbCr)N. The limited thermal stability of the solid solution is investigated in relation to several thermodynamic parameters. We suggest that the HEA designed multiprincipal element (AlTiVNbCr)N solid solutions are in a metastable state.

In the present study, the microstructure and wear mechanisms of texture controlled CVD α-Al2O3 layers with (001), (012) and (100) growth textures were investigated in single point turning of C45 carbon steel at low and high cutting speeds. The experimental coatings were investigated by FEG-SEM, EBSD and a combination of FIB and analytical TEM techniques prior to and after machining. Significant texture effects on wear performance of the α-Al2O3 coating layers were observed, confirming results from previous wear studies in the context of machining AISI 4140 carbon steel. The wear mechanisms of the coating layers were further interpreted in the light of thermal, mechanical and frictional conditions occurring at the tool–chip contact interface. Possible deformation mechanisms of the α-Al2O3 layers under the conditions of high pressure and temperatures acting on the tool surface are discussed. The high dislocation density revealed by the TEM observations in the subsurface α-Al2O3 layers was attributed to the activation of a basal slip deformation mechanism resulting from the combined action of the shear stress field and high temperature acting on the tool surface. It is suggested that the enhanced and more uniform near surface deformation capability of (001) α-Al2O3 is responsible for the improved machining performance.

Review of scientific instruments 90(10), 103901 - (2019). doi:10.1063/1.5091766, We present a custom built lathe designed for in operando high-energy x-ray scattering studies of thetool-chip and tool-workpiece contact zones during operation. The lathe operates at industriallyrelevant cutting parameters, i.e. at cutting speeds ≤ 400 m/min and feeds ≤ 0.3 mm/rev. By turningtests in carbon steel, performed at the high-energy material science beamline P07 at Petra III, DESY,Hamburg, we observe compressive strains in TiNbAlN and Al2O3/Ti(C,N) coatings on the tool flank faceduring machining. It is demonstrated that by the right choice of substrate and coating materials,diffraction patterns can be recorded and evaluated in operando, both from the tool-workpiece andtool-chip contacts, i.e. from the contact zones between the tool and the workpiece material on thetool flank- and rake faces, respectively. We also observe that a worn tool results in higher temperaturein the tool-chip contact zone compared to a new tool.This, Published by American Institute of Physics, [S.l.]

Varying the Si-content in Zr-Si-N coatings from 0.2 to 6.3 at.% causes microstructural changes from columnar to nanocomposite structure and a hardness drop from 37 to 26 GPa. The softer nanocomposite also displays lower fracture resistance. The tribological response of these coatings is investigated under different contact conditions, both at room and elevated temperatures. At room temperature tribooxidation is found to be the dominant wear mechanism, where the nanocomposite coatings display the lowest wear rate of 0.64 × 10 − 5 mm 3 /Nm, by forming an oxide diffusion barrier layer consisting of Zr, W, and Si. A transition in the dominant wear mechanism from tribooxidation to microploughing is observed upon increasing the test temperature and contact stress. Here, all coatings exhibit significantly higher coefficient of friction of 1.4 and the hardest coatings with columnar structure display the lowest wear rate of 10.5 × 10 − 5 mm 3 /Nm. In a microscopic wear test under the influence of contact-induced dominant elastic stress field, the coatings display wedge formation and pileup due to accumulation of the dislocation-induced plastic deformation. In these tests, the nanocomposite coatings display the lowest wear rate of 0.56 × 10 − 10 mm 3 /Nm, by constraining the dislocation motion.

Substoichiometric solid solution alloys of cubic (Ti1-xAlx)N-y with x = 0.26, 0.48 and 0.60, and y ranging from 0.93 to 0.75 were grown by cathodic arc deposition. The influence of nitrogen deficie ...

The phase evolution of cubic (c), solid solution TixCr-0.37Al1-0.37-x N alloys with x = 0.03 and 0.16, and the kinetics of the hexagonal (h)-AlN formation are studied via in situ wide angle x-ray scattering experiments during high temperature (1000-1150 degrees C) annealing. Spinodal decomposition was observed in Ti0.16Cr0.36Al0.48N while Ti0.03Cr0.38Al0.59N decomposes through nucleation and growth of h-AlN, c-TiN and c-CrAlN. h-AlN is formed from c-CrAlN domains in both cases and the formation rate of h-AlN depends on the stability of the c-CrAlN domains. In Ti0.16Cr0.36Al0.48N, the c-CrAlN domains are stabilized by crystallographic coherency with the surrounding c-TiCrN in a microstructure originating from spinodal decomposition. This results in lower formation rates of h-AlN for this composition. These differences are reflected in higher activation energy for h-AlN formation in Ti0.16Cr0.36Al0.48N compared to Ti0.03Cr0.38Al0.59N. It also points out different stabilities of the intermediate phase c-CrAlN during phase decomposition of TiCrAlN alloys. Additional contributions to the low activation energy for formation of h-AlN in Ti0.03Cr0.38Al0.59N stems from precipitation at grain boundaries. (C) 2016 Elsevier B.V. All rights reserved. Funding Agencies|EUs Erasmus-Mundus graduate school in Material Science and Engineering (DocMASE); Swedish Research Council VR [621- 2012-4401]; Rontgen-Angstrom Cluster grant [VR 2011-6505]; Swedish Foundation for Strategic Research, SSF [RMA08-0069]; Swedish government strategic research area grant AFM - SFO MatLiU [2009-00971]; VINNOVA (M - Era.net project) [2013-02355]

Aspects on the phase stability and mechanical properties of nitrogen deficient (Ti0.54Al0.46)N-y alloys were investigated. Solid solution alloys of (Ti,Al)N were grown by cathodic arc deposition. The kinetic energy of the impinging ions was altered by varying the substrate bias voltage from -30V to -80 V. Films deposited with a high bias value of -80V showed larger lattice parameter, finer columnar structure, and higher compressive residual stress resulting in higher hardness than films biased at -30V when comparing their as-deposited states. At elevated temperatures, the presence of nitrogen vacancies and point defects (anti-sites and self-interstitials generated by the ion-bombardment during coating deposition) in (Ti0.54Al0.46)N-0.87 influence the driving force for phase separation. Highly biased nitrogen deficient films have point defects with higher stability during annealing, which cause a delay of the release of the stored lattice strain energy and then accelerates the decomposition tendencies to thermodynamically stable c-TiN and w-AlN. Low biased nitrogen deficient films have retarded phase transformation to w-AlN, which results in the prolongment of age hardening effect up to 1100 degrees C, i.e., the highest reported temperature for Ti-Al-N material system. Our study points out the role of vacancies and point defects in engineering thin films with enhanced thermal stability and mechanical properties for high temperature hard coating applications. Published by AIP Publishing. Funding Agencies|European Unions Erasmus Mundus doctoral program in Materials Science and Engineering (DocMASE); Swedish Research Council [621-2012-4401]; Swedish government strategic research area grant AFM - SFO MatLiU [2009-00971]; VINNOVA [2013-02355]; DFG; federal state government of Saarland [INST 256/298-1 FUGG]; European Regional Development Fund [AME-Lab C/4-EFRE-13/2009/Br]

Reactive cathodic arc deposition was used to grow substoichiometric solid solution cubic c-(Ti1-xAlx)N-y thin films. The films were removed from the substrate and then heated in an argon environment to 1400 degrees C. Via solid state reactions, formation of MAX phase Ti4AlN3 was obtained. Additional phases such as Ti2AlN, c-TiN, w-AIN, Al5Ti2 and Al3Ti were also present during the solid state reaction. Ti4AlN3 formation was observed in samples with an Al metal fraction x amp;lt; 0.63 and a nitrogen content 0.4 amp;lt; y amp;lt; 0.6. Regardless of the initial composition, formation of Ti4AlN3 started in Ti2AlN crystal plates in the temperature range between 1200 and 1400 degrees C. Accompanying the onset of Ti4AlN3 was the presence of an intermediate structure identified as Ti6Al2N4, consisting of alternating layers of intergrown Ti2AlN and Ti4AlN3 phases with a half-unit-cell stacking. We suggest that the formation of Ti4AlN3 occurred via intercalation of aluminum and nitrogen along the basal plane accompanied by a simultaneous detwinning process. In addition we propose that this formation mechanism can be used to obtain MAX phases of high n order. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. Funding Agencies|European Unions Erasmus Mundus doctoral program DocMASE; Swedish Research Council [621-2012-4401]; Swedish government strategic research area grant AFM SFO MatLiU [2009-00971]; VINNOVA (M - Era.net project MC2) [2013-02355]; European Research Council under the European Communitys Seventh Framework Program (FP) [335383]; DFG; federal state government of Saarland [INST 256/298-1 FUGG, INST 256/431-1 FUGG]; European Regional Development Fund [AME-Lab C/4-EFRE-13/2009/Br]

Reactive RF-magnetron sputtering is used to grow Cr0.28Zr0.10O0.61 coatings at 500 degrees C. Coatings are annealed at 750 degrees C, 810 degrees C, and 870 degrees C. The microstructure evolution of the pseudobinary oxide compound is characterized through high resolution state of the art HRSTEM and HREDX-maps, revealing the segregation of Cr and Zr on the nm scale. The as-deposited coating comprises cc-(Cr,Zr)(2)O-3 solid solution with a Zr-rich (Zr,Cr)O-x. amorphous phase. After annealing to 750 degrees C tetragonal ZrO2 nucleates and grows from the amorphous phase. The ZrO2 phase is stabilized in its tetragonal structure at these fairly low annealing temperatures, possibly due to the small grain size (below 30 nm). Correlated with the nucleation and growth of the tetragonal-ZrO2 phase is an increase in hardness, with a maximum hardness after annealing to 750 degrees C, followed by a decrease in hardness upon coarsening, bcc metallic Cr phase formation and loss of oxygen, during annealing to 870 degrees C. The observed phase segregation opens up future design routes for pseudobinary oxides with tunable microstructural and mechanical properties. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. Funding Agencies|Swedish Research Council (VR) [621-212-4368, 330-2014-6336]; AB Sandvik Coromant; Karlsruhe Nano Micro Facility (KNMF); Helmholtz research infrastructure at Karlsruhe Institute of Technology (KIT); Marie Sklodowska Curie Actions, Cofund [INCA 600398]; Knut and Alice Wallenberg Foundation

In this study, the correlation existing among grinding, surface integrity, and flexural strength is investigated for WC-Co cemented carbides (hardmetals). A fine-grained WC-13 wt % Co grade and three different surface conditions: (1) ground, (2) mirror-like polished (reference), and (3) ground plus high-temperature annealed, are investigated. Surface integrity and mechanical characterization is complemented with fractography. The grinding strongly affects both surface integrity and flexural strength. During grinding, a damaged thin layer together with high compressive residual stresses is introduced. The layer results in considerable strength enhancement compared to the reference polished surface condition. Fractography reveals that the improved strength mainly stems from grinding-induced changes on effective location, from surface into subsurface levels, of the strength-controlling flaw.

The structure, growth, and phase stability of (Ti1-x,Alx)N films with high Al content were investigated. (Ti1-x,Alx)N (x = 0.63 and 0.77) thin films were grown on MgO(111) substrates at 700 °C using a UHV DC magnetron sputtering system. The (Ti0.37,Al0.63)N film is a single crystal with a cubic NaCl (B1) structure while the (Ti0.23,Al0.77)N film only shows epitaxial growth of the same cubic phase in the first few atomic layers. With increasing film thickness, epitaxial wurtzite (B4) forms. The thin cubic layer and the wurtzite film has an orientation relationship of c-(Ti0.23,Al0.77)N 111 1 1 ¯ 0 ǀǀw-(Ti0.23,Al0.77)N 0001 11 2 ¯ 0 . Continued deposition results in a gradual break-down of the epitaxial growth. It is replaced by polycrystalline growth of wurtzite columns with a high degree of 0001 texture, separated by a Ti-enriched cubic phase. In the as-deposited state, c-(Ti0.27,Al0.63)N displays a homogeneous chemical distribution while the w-(Ti0.23,Al0.77)N has segregated to Al- and Ti-rich domains. Annealing at 900 °C resulted in the spinodal decomposition of the metastable c-(Ti0.27,Al0.63)N film and formation of coherent elongated c-AlN and c-TiN-rich domains with an average width of 4.5 ± 0.2 nm while the width of the domains in the w-(Ti0.23,Al0.77)N film only marginally increases to 2.8 ± 0.1 nm. The slower coarsening rate of the wurtzite structure compared to cubic is indicative of a higher thermal stability.

Heteroepitaxial c-(Ti-0.37,Al-0.63)N thin films were grown on MgO(001) and MgO(111) substrates using reactive magnetron sputtering. High resolution high-angle annular dark-field scanning transmissi ...

article i nfo Anisotropy effects on the spinodal decomposition in cathodic arc evaporated cubic "phase c-Ti1−xAlxN coatings have been studied with respect to composition, microstructure and hardness properties before and after a con- tinuous turning operation.Coatings are simultaneously being exposed toboth a hightemperatureand high pres- sure during the metal cutting process. As evident from the current results, a high Al content coating, x = 0.66, when exposed to such extreme conditions decomposes into cubic c-AlN and c-TiN-rich domains. In this case, the evolving microstructure comprises interconnected spatially periodic, elongated and coherent cubic c-AlN and c-TiN-rich regions aligned along elastic compliant b100N crystal direction. A significantly different micro- structure with randomly oriented domains is observed for a coating with an elemental composition closer to the isotropic limit, x = 0.28, exposed under the same conditions. From a coating hardness perspective, the nanoindentation results display a minor age hardening effect for the c-Ti1−xAlxN coating grown at x = 0.28 while the coating grown with x = 0.66 exhibits a significant age-hardening effect of about 18%. We conclude that both microstructure and age hardening behavior during spinodal decomposition of c-Ti1−xAlxN correlate totherelativeamountofmetal Ti/Al ratioand consequentlytothe elastic anisotropy oftheas-growncoatingma- terial. These results provide new insights to the understanding of improved wear resistance of c-Ti1−xAlxN with Al content during metal cutting.

The influence of the Ti–Si cathode grain size on cathodic arc processes and resulting Ti–Si–N coating synthesis has been studied. 63 mm Ti–Si cathodes containing 20–25 at.% Si with four dedicated grain size of ~ 8 μm, ~ 20 μm, ~ 110 μm, and ~ 600 μm were fabricated via spark plasma sintering or hot isostatic pressing. They were evaporated in 2 Pa nitrogen atmosphere in an industrial-scale arc deposition system and the Ti–Si–N coatings were grown at 50 A, 70 A, and 90 A arc currents. The composition and microstructure of the virgin and worn cathode surfaces as well as the resulting coatings were characterized using optical and electron microscopy, X-ray diffraction, elastic recoil detection analysis, X-ray photoelectron spectroscopy, and nanoindentation. The results show that the existence of multiple phases with different work function values directly influences the cathode spot ignition behavior and also the arc movement and appearance. Specifically, there is a preferential erosion of the Ti5Si3-phase grains. By increasing the grain size of the virgin cathode, the preferential erosion is enhanced, such that the cathode surface morphology roughens substantially after 600 Ah arc discharging. The deposition rate of the Ti–Si–N coating is increased with decreasing grain size of the evaporated Ti–Si cathodes. The droplet number density and the droplet shape of the coatings are influenced by the arc movement, which is also shown to depend on the cathode grain size.

The cracking and delamination of TiN-coated hardmetals (WC-Co cemented carbides) when subjected to Brale indentation were studied. Experimental variables were substrate microstructure related to low (6 wt% Co) and medium (13 wt% Co) binder content, and surface finishes associated with grinding and polishing stages before film deposition. Brale indentation tests were conducted on both coated and uncoated hardmetals. Emphasis has been placed on assessing substrate microstructure and subsurface finish effects on load levels at which cracking and delamination phenomena emerge, the type of cracking pattern developed, and how fracture mechanisms evolve with increasing load. It is found that polished and coated hardmetals are more brittle (radial cracking) and the adhesion strength (coating delamination) diminishes with decreasing binder content. Such a response is discussed on the basis of the influence of intrinsic hardness/brittleness of the hardmetal substrate on both cracking at the subsurface level and effective stress state, particularly regarding changes in shear stress component. Grinding promotes delamination compared to the polished condition, but strongly inhibits radial cracking. This is a result of the interaction between elastic-plastic deformation imposed during indentation and several grinding-induced effects: remnant compressive stress field, pronounced surface texture and micro cracking within a thin altered subsurface layer. As a consequence, coating spallation prevails over radial cracking as the main mechanism for energy dissipation in ground and coated hardmetals. (C) 2016 Elsevier B.V. All rights reserved. Funding Agencies|Spanish MINECO [MAT 2012-34602]; Erasmus Mundus joint European Doctoral Programme DocMASE

We present an industry-relevant, large-scale, ultra-high vacuum (UHV) magnetron sputtering and cathodic arc deposition system purposefully designed for time-resolved in situ thin film deposition/annealing studies using high-energy (greater than50 keV), high photon flux (greater than10(12) ph/s) synchrotron radiation. The high photon flux, combined with a fast-acquisition-time (less than1 s) two-dimensional (2D) detector, permits time-resolved in situ structural analysis of thin film formation processes. The high-energy synchrotron-radiation based x-rays result in small scattering angles (less than11 degrees), allowing large areas of reciprocal space to be imaged with a 2D detector. The system has been designed for use on the 1-tonne, ultra-high load, high-resolution hexapod at the P07 High Energy Materials Science beamline at PETRA III at the Deutsches Elektronen-Synchrotron in Hamburg, Germany. The deposition system includes standard features of a typical UHV deposition system plus a range of special features suited for synchrotron radiation studies and industry-relevant processes. We openly encourage the materials research community to contact us for collaborative opportunities using this unique and versatile scientific instrument. (C) 2015 AIP Publishing LLC. Funding Agencies|Swedish Research Council via the Rontgen Angstrom Cluster (RAC) Frame Program [2011-6505]; German Federal Ministry of Education and Research (BMBF) [05K12CG1]

In this study, the influence of substrate surface finish on scratch resistance and associated failure mechanisms is investigated in the case of a TiN-coated hardmetal. Three different surface finish conditions are studied: as-sintered (AS), ground (G), and mirror-like polished (P). For G conditioned samples, scratch tests are conducted both parallel and perpendicular to the direction of the grinding grooves. It is found that coated AS, G and P samples exhibit similar critical load for initial substrate exposure and the same brittle adhesive failure mode. However, the damage scenarios are different, i.e. the substrate exposure is discrete and localized to the scratch tracks for G samples while a more pronounced and continuous exposure is seen for AS and P ones. Aiming to understand the role played by the grinding-induced compressive residual stresses, the study is extended to coated systems where ground substrates are thermal annealed (for relieving stresses) before being ion etched and coated. It yielded lower critical loads and changes in the mechanisms for the scratch-related failure; the latter depending on the relative orientation between scratching and grinding directions.

In this study we explore the cutting performance of ZrAlN coatings. WC:Co cutting inserts coated by cathodic arc evaporated Zr1-xAlxN coatings with x between 0 and 0.83 were testeciin a longitudinal turning operation. The progress of wear was studied by optical microscopy and the used inserts were studied by electron microscopy. The cutting performance was correlated to the coating composition and the best performance was found for the coating with highest Al-content consisting of a wurtzite ZrAlN phase which is assigned to its high thermal stability. Material from the work piece was observed to adhere to the inserts during turning and the amount of adhered material and its chemical composition is independent on the Al-content of the coating. (C) 2015 Elsevier B.V. All rights reserved. Funding Agencies|Vinnova (Swedish Governmental Agency for Innovation Systems) through the VINN Excellence Center on Functional Nanoscale Materials (Fun Mat)

Zr-Si-N films with varying Si contents were grown on WC-Co substrates by reactive cathodic arc deposition technique. The resulting microstructures of the films correlate to dominant variation in mechanical properties and deformation mechanisms. Si forms a substitutional solid solution in the cubic ZrN lattice up to 1.8 at.% exhibiting a fine columnar microstructure. Further Si additions result in precipitation of an amorphous (a)-SiNx phase and evolution of a nanocomposite microstructure (nc ZrN/a-SiNx) which completely suppresses the columnar microstructure at 63 at.% Si. The rotation-induced artificial layering during film growth is used as a marker to visualize the deformation of the film. A dislocation-based homogeneous plastic deformation mechanism dominates the columnar microstructure, while grain boundary sliding is the active mechanism mediating heterogeneous plastic deformation in the nanocomposite microstructure. Film hardness increases with increasing Si content in the columnar microstructure due to an effective solid solution strengthening. The deformation mechanism of localized grain boundary sliding in the nanocomposite microstructure results in a lower hardness. When cracking is induced by indentation, the fine columnar microstructure exhibits pronounced crack deflection that results in a higher fracture resistance compared to the nanocomposite films. (C) 2014 Elsevier B.V. All rights reserved.

In the present work, we have studied the decomposition of arc evaporated Ti0.55Al0.45N and Ti0.36Al0.64N during heat treatment in vacuum by in-situ synchrotron wide angle x-ray scattering primarily to characterize the kinetics of the phase transformation of AlN from the cubic NaCl-structure to the hexagonal wurtzite-structure. In addition, in-situ small angle x-ray scattering measurements were conducted to explore details of the wavelength evolution of the spinodal decomposition, thus providing information about the critical size of the c-AlN rich domains prior to the onset of the h-AlN transformation. We report the fractional cubic to hexagonal transformation of AlN in Ti1-xAlxN as a function of time and extract activation energies between 320 and 350 kJ/mol dependent on alloy composition. The onset of the hexagonal transformation occurs at about 50 K lower temperature in Ti0.36Al0.64N compared to Ti0.55Al0.45N where the high Al content alloy also has a significantly higher transformation rate. A critical wavelength for the cubic domains of about 13 nm was observed for both alloys. Scanning transmission electron microscopy shows a c-TiN/h-AlN microstructure with a striking morphology resemblance to the c-TiN/c-AlN microstructure present prior to the hexagonal transformation. On the day of the defence date of the thesis the status of this article was Manuscript.

In this work we present the cutting performance of Ti0.50Al0.50N coatings which have been deposited with both a fixed and an alternating bias of − 35 V and − 70 V together with a Ti0.33Al0.67N reference coating grown at − 35 V. During deposition of the bias-layered coatings, the bias was instantaneously changed with four different bias-layer periods ranging from approximately 250 to 1500 nm. For the layers deposited with a fixed bias, a transition from a (100) to a (111) preferred orientation was observed with the change in bias from − 35 V to − 70 V. The coatings grown with an alternating bias, however, show a (111) preferred orientation with an intensity that slightly depends on bias-layer period. Metal cutting tests were performed in 100Cr6 steel with a cutting speed of 200 m/min, a feed of 0.2 mm/rev and a depth of cut of 2 mm. The wear resistance was quantified in terms of crater and flank wear resistance showing an improvement for all bias-layered coatings. This is attributed to a (111) oriented refined grain structure in combination with low residual stresses in the coating.

Ti(1−x−y)AlxSiyNz (0.02≤x≤0.46, 0.02≤y≤0.28, and 1.08≤z≤1.29) thin films were grown on cemented carbide substrates in an industrial scale cathodic arc evaporation system using Ti-Al-Si compound cathodes in a N2 atmosphere. The microstructure of the as-deposited films changes from nanocrystalline to amorphous by addition of Al and Si to TiN. Upon incorporation of 12 at% Si and 18 at% Al, the films assume an x-ray amorphous state. Post-deposition anneals show that the films are thermally stable up to 900 ◦C. The films exhibit age hardening up to 1000 ◦C with an increase in hardness from 21.9 GPa for as-deposited films to 31.6 GPa at 1000 ◦C. At 1100 ◦C severe out-diffusion of Co and W from the substrate occur, and the films recrystallize into c-TiN and w-AlN.

This paper describes details of the spinodal decomposition and coarsening in metastable cubic Ti0.33Al0.67N and Ti0.50Al0.50N coatings during isothermal annealing, studied by in-situ small angle x-ray scattering, in combination with phase field simulations. We show that the isostructural decomposition occurs in two stages. During the initial stage, spinodal decomposition, of the Ti0.50Al0.50N alloy, the phase separation proceeds with a constant compositional wavelength of � 2.8nm of the AlN- and TiN-rich domains. The time for spinodal decomposition depends on annealing temperature as well as alloy composition. After the spinodal decomposition, the coherent cubic AlN- and TiN-rich domains coarsen. The coarsening rate is kinetically limited by diffusion, which allowed us to estimate the diffusivity and activation energy of the metals to 1.4 � 10 � 6 m 2 s � 1 and 3.14eV at � 1 , respectively. V C 2013 AIP Publishing LLC .[ http://dx.doi.org/10.1063/1.4809573]

Through a combination of theoretical and experimental observations we study the high temperature decomposition behavior of c-(TixZryAlzN) alloys. We show that for most concentrations the high formation energy of (ZrAl)N causes a strong tendency for spinodal decomposition between ZrN and AlN while other decompositions tendencies are suppressed. In addition we observe that entropic effects due to configurational disorder favor a formation of a stable Zr-rich (TiZr)N phase with increasing temperature. Our calculations also predict that at high temperatures a Zr rich (TiZrAl)N disordered phase should become more resistant against the spinodal decomposition despite its high and positive formation energy due to the specific topology of the free energy surface at the relevant concentrations. Our experimental observations confirm this prediction by showing strong tendency towards decomposition in a Zr-poor sample while a Zr-rich alloy shows a greatly reduced decomposition rate, which is mostly attributable to binodal decomposition processes. This result highlights the importance of considering the second derivative of the free energy, in addition to its absolute value in predicting decomposition trends of thermodynamically unstable alloys. On the day of the defence date the status of this article was Manuscript.

The influence of the cathode grain size and the substrate fixturing on the microstructure evolution of the Cr cathodes and the resulting Cr-N coating synthesis is studied. Hot isostatic pressed Cr ...

The effect of metal alloying on mechanical properties including hardness and fracture toughness were investigated in three alloys, Ti~0.33Al0.50(Me)~0.17N (Me¿=¿Cr, Nb and V), and compared to Ti0.50Al0.50N, in the as-deposited state and after annealing. All studied alloys display similar as-deposited hardness while the hardness evolution during annealing is found to be connected to phase transformations, related to the alloy's thermal stability. The most pronounced hardening was observed in Ti0.50Al0.50N, while all the coatings with additional metal elements sustain their hardness better and they are harder than Ti0.50Al0.50N after annealing at 1100¿°C. Fracture toughness properties were extracted from scratch tests. In all tested conditions, as-deposited and annealed at 900 and 1100¿°C, Ti0.33Al0.50Nb0.17N show the least surface and sub-surface damage when scratched despite the differences in decomposition behavior and h-AlN formation. Theoretically estimated ductility of phases existing in the coatings correlates well with their crack resistance. In summary, Ti0.33Al0.50Nb0.17N is the toughest alloy in both as-deposited and post-annealed states.

Ground hardmetals are exposed to high temperatures during both processing (e.g. coating deposition) and use (e.g. as a cutting tool). However, studies on thermally induced changes of surface integrity are limited. Here we address this by means of FIB/FESEM and EBSD investigation, with special focus on the binder phase characterization. Our findings indicate that thermal treatment causes two main surface modifications. First, an unexpected microporosity appears in the binder within the subsurface layer when ground surfaces are heated. Second, the metallic phase underneath the ground surface experiences metallurgical changes, in terms of grain and crystallographic phase structures. The mechanisms responsible for these modifications of the binder are discussed in terms of grinding-induced and thermally-reversed phase transformation as well as recrystallization phenomena. We also note that no additional heat treatment related changes such as microcracking and carbide fragmentation in the subsurface layer, are discerned.

Contact loading is a common service condition for coated hardmetal tools and components. Substrate grinding represents a key step within the manufacturing chain of these coated systems. Within this context, the influence of surface integrity changes caused by abrasive grinding of the hardmetal substrate, prior to coating, is evaluated with respect to contact damage resistance. Three different substrate surface finish conditions are studied: ground (G), mirror-like polished (P) and ground plus heat-treated (GTT). Tests are conducted by means of spherical indentation under increasing monotonic load and the contact damage resistance is assessed. Substrate grinding enhances resistance against both crack nucleation at the coating surface and subsequent propagation into the hardmetal substrate. Hence, crack emergence and damage evolution is effectively delayed for the coated G condition, as compared to the reference P one. The observed system response is discussed on the basis of the beneficial effects associated with compressive residual stresses remnant at the subsurface level after grinding, ion-etching and coating. The influence of the stress state is further corroborated by the lower contact damage resistance exhibited by the coated GTT specimens. Finally, differences observed on the interaction between indentation-induced damage and failure mode under flexural testing points in the direction that substrate grinding also enhances damage tolerance of the coated system when exposed to contact loads

Manufacturing of hardmetal tools often involves surface grinding, ion etching and final coating. Each stage throughout the manufacturing chain introduces surface integrity changes which may be critical for defining the final mechanical behavior of the coated tools. Within this context, an experimental test program has been developed to assess the influence of a coating (TiN) deposition on surface integrity and transverse rupture strength of a previously ground fine-grained WC-Co grade substrate. Four different substrate surface finish conditions (prior to ion etching and coating) were evaluated: as sintered (AS), ground (G), polished (P), and ground plus high temperature annealing (GTT). Surface integrity and fracture resistance characterization, complemented with a detailed fractographic analysis, were performed on both uncoated and coated samples. Results show that the surface integrity after grinding has been partly modified during the ion etching and film deposition processes, particularly in terms of a reduced compressive residual stress state at the substrate surface level. Consequently, the grinding induced strength enhancement in hardmetals is reduced for coated specimens. Main reason behind it is the change of nature, location and stress state acting on critical flaw: from processing defects existing at the subsurface (uncoated G specimens) to grinding-induced microcracks located close to the interface between coating and substrate, but within the subsurface of the latter (coated G specimens). This is not the case for AS and P conditions, where flexural strength does not change as a result of ion etching and coating. Finally, fracture resistance increases slightly for GTT specimens after coating process, possibly caused by a beneficial effect of the deposited film on the residual stress state at the surface.