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Effects of nitrogen vacancies on phase stability and mechanical properties of arc deposited (Ti0.52Al0.48)Ny (y<1) coatings
Linköping University, Department of Physics, Chemistry and Biology, Nanostructured Materials. Linköping University, Faculty of Science & Engineering.
Functional Materials, Department Materials Science, Saarland University, Saarbrucken, Germany.
Linköping University, Department of Physics, Chemistry and Biology, Nanostructured Materials. Linköping University, Faculty of Science & Engineering. SECO Tools AB, Fagersta, Sweden.ORCID iD: 0000-0003-4577-0976
Functional Materials, Department Materials Science, Saarland University, Saarbrucken, Germany.
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2017 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 330, no Supplement C, p. 77-86Article in journal (Refereed) Published
Abstract [en]

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 present a columnar structure with decreasing column widths from 250 to 60nm, due to a corresponding reduced N content, accompanied by changes in preferred orientation from 200 to 111 to 220. Among these, coatings prepared with 0.92≥y≥0.75 exhibit spinodal decomposition and consequently age hardening at elevated temperatures. A reduced N content upshifts the hardness maximum by >300 °C. For these samples, the high temperature treatment resulted in interdiffusion of substrate elements, Co and C, mainly along column boundaries. Nevertheless, no detrimental effect in the hardness could be correlated. Conversely, a low N content sample (y=0.46) presents significant lattice diffusion of substrate elements Co, C, W, and Ta in the coating. In this case, the substrate elements are present throughout the coating, forming additional phases such as c-Ti(C,N), c-Co(Al,Ti,W), and c-(Ti,W,Ta)(C,N), with an observed increased hardness from 16 to 25GPa. We suggest that the substitution of nitrogen by carbon and the solution of W and Ta in c-TiN are responsible for the observed hardening. Our investigation shows the potential of sub-stoichiometric (Ti1-xAlx)Ny coatings for high temperature applications such as cutting tools and puts forth corresponding criteria for N content selection.

Place, publisher, year, edition, pages
Elsevier, 2017. Vol. 330, no Supplement C, p. 77-86
Keywords [en]
TiAlN, Thin films, Nitrogen vacancies, Spinodal decomposition, Age hardening
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:liu:diva-142115DOI: 10.1016/j.surfcoat.2017.09.043ISI: 000414819700010Scopus ID: 2-s2.0-85030314026OAI: oai:DiVA.org:liu-142115DiVA, id: diva2:1151242
Note

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 grant) [2013-02355]; DFG [INST 256/298-1 FU

Available from: 2017-10-23 Created: 2017-10-23 Last updated: 2018-01-03Bibliographically approved
In thesis
1. Defect-engineered (Ti,Al)N thin films
Open this publication in new window or tab >>Defect-engineered (Ti,Al)N thin films
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis investigates the effect of point defects (nitrogen vacancies and interstitials) and multilayering ((Ti,Al)N/TiN) on the phase transformations in cathodic arc-evaporated cubic (Ti,Al)N thin films at elevated temperatures. Special attention is paid to the evolution of the beneficial spinodal decomposition into c-TiN and c-AlN, the detrimental formation of wurtzite AlN and the potential application as hard coating in cutting tools.

c-(Ti1-xAlx)Ny thin films with varying Al fractions and N content (y = 0.93 to 0.75) show a delay in the spinodal decomposition when increasing the amount of N vacancies. This results in a 300 °C upshift in the age hardening and a delay in the w-AlN formation, while additions of self-interstitials enhance phase separation. High temperature interaction between hard metal substrates and thin films is more pronounced when increasing N deficiency through diffusion of substrate elements into the film. Low N content films (y = 0.58 to 0.40) showed formation of additional phases such as Ti4AlN3, Ti2AlN, Al5Ti2 and Al3Ti during annealing and a transformation from Ti2AlN to Ti4AlN3 via intercalation. The multilayer structure of TiN/TiAlN results in surfacedirected spinodal decomposition that affects the decomposition behavior. Careful use of these effects appears as a promising method to improve cutting tool performance.

Abstract [de]

Diese Arbeit untersucht den Effekt von Punktdefekten (Stickstoffleerstellen und Zwischengitteratome) und Multilagen ((Ti,Al)N/TiN) auf die Phasenumwandlung in lichtbogenverdampften kubischen (Ti,Al)N-Dünnschichten bei erhöhten Temperaturen. Besonderes Augenmerk liegt auf der Entwicklung der vorteilhaften spinodalen Entmischung in c-TiN und c-AlN und der nachteiligen Bildung von Wurtzit-AlN, sowie der möglichen Anwendung als Hartstoffbeschichtung von Schneidwerkzeugen.

c-(Ti1-xAlx)Ny mit unterschiedlichem Al-Anteil und N-Gehalten von y = 0,93 bis 0,75 zeigt mit zunehmenden Stickstoffleerstellen eine Verzögerung der spinodalen Entmischung. Dadurch verschiebt sich die Ausscheidungshärtung um 300 °C zu höheren Temperaturen und die w-AlN-Bildung wird verzögert, während der Einbau von Eigenzwischengitteratomen die Entmischung beschleunigt. Die Hochtemperaturwechselwirkung zwischen Hartmetallsubstrat und Dünnschicht durch Diffusion von Substratelementen in die Schicht nimmt mit steigendem Stickstoffdefizit zu. Stickstoffarme Schichten (y = 0,58 bis 0,40) zeigen während der Wärmebehandlung zusätzliche Phasen wie Ti4AlN3, Ti2AlN, Al5Ti2 und Al3Ti und eine Umwandlung von Ti2AlN in Ti4AlN3 durch Interkalation. Die Multischichtstruktur von TiN/TiAlN führt zu einer oberflächengerichteten spinodalen Entmischung, die das Entmischungsverhalten beeinflusst. Ein gezielter Einsatz dieser Effekte erscheint als ein vielsprechender Weg, um die Leistungsfähigkeit von Schneidwerkzeugen zu verbessern.

Abstract [sv]

I denna avhandling behandlas inverkan av punktdefekter (kvävevakanser och interstitialer) och multilagring ((Ti,Al)N/TiN) på högtemperaturfasomvandlingar i tunna arcförångade skikt av kubiska (Ti,Al)N. Störst vikt har lagts på utvecklingen av det fördelaktiga spinodala sönderfallet till c-TiN och c-AlN, den ofördelaktiga omvandlingen till w-AlN och potentialen som hårda skikt i verktygstillämpningar.

Tunna c-(Ti1-xAlx)Ny skikt med olika Al-andel och en N-halt mellan (y = 0.93 och 0.75) uppvisar ökad undertryckning av det spinodala sönderfallet med ökat kvävevakanshalt. Detta resulterar i bildandet av w-AlN skiftas upp i temperatur vilket gör att åldershärdningen höjs med 300 °C. Däremot medför närvaron av självinterstitialer ett snabbare sönderfall. Växelverkan mellan hårdmetallsubstraten och de tunna skikten vid hög temperatur ökar med minskad kvävehalt i skiten genom diffusion av atomer från substratet in i filmen. Filmer med låg kvävehalt (y = 0.58 till 0.40) bildar även andra faser så som Ti4AlN3, Ti2AlN, Al5Ti2 och Al3Ti under värmebehandling och fasomvandlingen från Ti2AlN till Ti4AlN3 sker via en mekanism kallad intercalation. Multilagring av TiN/TiAlN resulterar i ett ytriktad spinodalt sönderfall vilket påverkar det totala sönderfallsförloppet. Nyttjande av dessa resultat syns som lovande vägar till förbättrade verktygsegenskaper.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2017. p. 73
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1878
National Category
Physical Sciences
Identifiers
urn:nbn:se:liu:diva-142116 (URN)10.3384/diss.diva-142116 (DOI)9789176854563 (ISBN)
Public defence
2017-11-14, House D3 3, Saarland University, DE-66123 Saarbrücken, Germany, Saarbrücken, 14:15 (English)
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Supervisors
Available from: 2017-10-23 Created: 2017-10-23 Last updated: 2019-10-11Bibliographically approved

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Schramm, Isabella C.Johansson Jõesaar, Mats P.Odén, Magnus

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