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Inside The Miscibility Gap: Nanostructuring and Phase Transformations in Hard Nitride Coatings
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is concerned with self-organization phenomena in hard and wear resistant transition-metal nitride coatings, both during growth and during post deposition thermal annealing. The uniting physical principle in the studied systems is the immiscibility of their constituent parts, which leads, under certain conditions, to structural variations on the nanoscale. The study of such structures is challenging, and during this work atom probe tomography (apt) was developed as a viable tool for their study. Ti0.33Al0.67N was observed to undergo spinodal decomposition upon annealing to 900 °C, by the use of apt in combination with electron microscopy. The addition of C to TiSiN was found to promote and refine the feather-like microstructure common in the system, with an ensuing decrease in thermal stability. An age-hardening of 36 % was measured in arc evaporated Zr0.44Al0.56N1.20, which was a nanocomposite of cubic, hexagonal, and amorphous phases. Magnetron sputtering of Zr0.64Al0.36N at 900 °C resulted in a self-organized and highly ordered growth of a two-dimensional two-phase labyrinthine structure of cubic ZrN and wurtzite AlN.The structure was analyzed and recovered by apt, although the ZrN phase suffered from severe trajectory aberrations, rendering only the Al signal useable.The initiation of the organized growth was found to occur by local nucleation at 5-8 nm from the substrate, before which random fluctuations in Al/Zr content increased steadily from the substrate. Finally, the decomposition of solid-solution TiB0.33N0.67 was found, by apt, to progress through the nucleation of TiB0.5N0.5 and TiN, followed by the transformation of the former into hexagonal TiB2.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2012. , 69 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1472
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-84263ISBN: 978-91-7519-809-5 (print)OAI: oai:DiVA.org:liu-84263DiVA: diva2:558401
Public defence
2012-10-19, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2012-10-03 Created: 2012-10-03 Last updated: 2016-08-31Bibliographically approved
List of papers
1. Spinodal decomposition of Ti0.33Al0.67N thin films studied by atom probe tomography
Open this publication in new window or tab >>Spinodal decomposition of Ti0.33Al0.67N thin films studied by atom probe tomography
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2012 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 520, no 13, 4362-4368 p.Article in journal (Refereed) Published
Abstract [en]

Details of the phase decomposition in NaCl-structure Ti0.33Al0.67N thin films deposited by cathodic arc evaporation are studied by atom probe tomography. We demonstrate that as-deposited films are in the earliest stage of decomposition for which electron microscopy and x-ray diffraction indicate a single-phase solid solution. Annealing at 900 degrees C further activates spinodal decomposition of the films, although pockets of unde-composed material remain after 2 h. N preferentially segregates to the AlN and TiN domains, causing the TiAlN matrix to be understoichiometric, by the energetics of N vacancies in TiAlN. The corresponding modulation in stoichiometry implies a Kirkendall effect, caused by different Al and Ti diffusivities.

Place, publisher, year, edition, pages
Elsevier, 2012
Keyword
Titanium aluminum nitride, Spinodal decomposition, Atom probe tomography, Thin films
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-77325 (URN)10.1016/j.tsf.2012.02.085 (DOI)000303084200023 ()
Note

Funding Agencies|Swedish Research Council||VINN Excellence Center on Functional Nanoscale Materials||

Available from: 2012-05-11 Created: 2012-05-11 Last updated: 2017-12-07Bibliographically approved
2. Microstructure evolution and age hardening in (Ti,Si)(C,N) thin films deposited by cathodic arc evaporation
Open this publication in new window or tab >>Microstructure evolution and age hardening in (Ti,Si)(C,N) thin films deposited by cathodic arc evaporation
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2010 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 519, no 4, 1397-1403 p.Article in journal (Refereed) Published
Abstract [en]

Ti1 − xSixCyN1 − y films have been deposited by reactive cathodic arc evaporation onto cemented    carbide substrates. The films were characterized by X-ray diffraction, elastic recoil detection analysis, transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron-energy loss spectroscopy and nanoindentation. Reactive arc evaporation in a mixed CH4 and N2 gas gave    films with 0 ≤ x ≤ 0.13 and 0≤y≤0.27. All films had the NaCl-structure with a dense columnar microstructure, containing a featherlike pattern of nanocrystalline grains for high Si and C contents. The film hardness was 32–40GPa. Films with x > 0 and y > 0 exhibited age-hardening up to 35–44 GPa when isothermally annealed up to 900 °C. The temperature threshold for over-ageing was decreased to 700 °C with increasing C and Si content, due to migration of Co, W and Cr from the substrate to the film, and loss of Si. The diffusion pathway was tied to grain boundaries provided by the featherlike substructure.

Keyword
Age hardening, Transmission Electron Microscopy, Thin films, TiSiCN, Arc evaporation, Mechanical properties
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-60522 (URN)10.1016/j.tsf.2010.08.150 (DOI)000285125300024 ()
Available from: 2010-10-15 Created: 2010-10-15 Last updated: 2017-12-12Bibliographically approved
3. Age hardening in arc-evaporated ZrAlN thin films
Open this publication in new window or tab >>Age hardening in arc-evaporated ZrAlN thin films
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2010 (English)In: Scripta Materialia, ISSN 1359-6462, E-ISSN 1872-8456, Vol. 62, no 10, 739-741 p.Article in journal (Refereed) Published
Abstract [en]

Zr0.44Al0.56N1.20 films were deposited by reactive arc evaporation on WC-Co substrates. As-deposited films have a defect-rich NaCl-cubic and wurtzite phase mixture. During annealing at 1100 degrees C the films undergo simultaneous recovery of the ZrN-rich c-ZrAlN nanoscale domains and formation of semicoherent w-ZrAlN nanobricks, while the excess nitrogen is released. This process results in an age hardening effect as high as 36%, as determined by nanoindentation. At 1200 degrees C, the w-AlN recrystallizes and the hardening effect is lost.

Place, publisher, year, edition, pages
Amsterdam: Elsevier Science B.V., 2010
Keyword
PVD, Nanoindentation, TEM, Hardness, Thin films
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-54847 (URN)10.1016/j.scriptamat.2010.01.049 (DOI)000276295800004 ()
Available from: 2010-04-16 Created: 2010-04-16 Last updated: 2017-12-12Bibliographically approved
4. Self-organized Labyrinthine Nanostructure in Zr0.64Al0.36N Thin Films
Open this publication in new window or tab >>Self-organized Labyrinthine Nanostructure in Zr0.64Al0.36N Thin Films
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Self-organization of functional ceramics on the nanometer scale drives scientific and technological research in such diverse fields as cutting tools and light-emitting diodes. A classic example is spinodal decomposition in TiAlN thin films, which yields intricate nanostructures from the isostructural decomposition into cubic-structrure (c) AlN and TiN domains, resulting in age hardening [1]. Here, we explore the ZrN-AlN system, which has one of the largest positive enthalpies of mixing among the systems combining a transition metal nitride and a wide-band gap nitride [2]. Interestingly, an original nanolabyrinthine structure evolves during thin film synthesis of Zr0.64Al0.36N. It consists of the non-isostructural phases c-ZrN and wurtzite-AlN with standing {110}‖{112̄0} planes.The selforganization in this system is discussed in terms of a competition between interfacial and surface elastic energy, which produces a structure with a well-defined length scale. This effective nanostructural design yields films with hardnesses of 36 GPa, 44 % higher than comparable ZrN films.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-84257 (URN)
Available from: 2012-10-03 Created: 2012-10-03 Last updated: 2016-08-31Bibliographically approved
5. Self-organized Nanostructuring in Zr0.64Al0.36N Thin Films Studied by Atom Probe Tomography
Open this publication in new window or tab >>Self-organized Nanostructuring in Zr0.64Al0.36N Thin Films Studied by Atom Probe Tomography
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2016 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, 233-238 p.Article in journal (Refereed) Published
Abstract [en]

We have applied atom probe tomography (apt) to analyze the selforganized structure of wear-resistant Zr0.64Al0.36N thin films grown by magnetron sputtering. Transmission electron microscopy shows that these films grow as a two-dimensional nanocomposite, consisting of interleaved lamellae in a labyrinthine structure, with a size scale of ∼ 5 nm. The structure was recovered in the Al apt signal, while the Zr and N data lacked structural information due to severe local magnification effects. The onset of the self-organized growth was observed to occur locally by nucleation, at 5-8 nm from the MgO substrate, after increasing Zr-Al compositional fluctuations. Finally, it was observed that the self-organized growth mode could be perturbed by renucleation of ZrN.

Place, publisher, year, edition, pages
Elsevier, 2016
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-84258 (URN)10.1016/j.tsf.2016.07.034 (DOI)000381939700037 ()
Note

Funding agencies: VINN Excellence Center on Functional Nanoscale Materials; Swedish Research Council; Swedish Government Strategic Faculty Grant in Materials Science (SFO Mat-LiU) at Linkoping University; Swedish Governmental Agency for Innovation Systems (Vinnova) [2011-0

Vid tiden för disputationen förelåg publikationen som manuskript

Available from: 2012-10-03 Created: 2012-10-03 Last updated: 2017-12-07Bibliographically approved
6. Phase Transformation of Ti(B,N) into TiB2 and TiN Studied by Atom Probe Tomography
Open this publication in new window or tab >>Phase Transformation of Ti(B,N) into TiB2 and TiN Studied by Atom Probe Tomography
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

The phase transformation of supersaturated solid-solution cubic (c) Ti0.57(B0.28N0.72)0.43 thin films into the equilibrium phases TiN and TiB2 has been studied by a combination of X-ray diffraction, transmission electron microscopy, and atom probe tomography. The transformation was found to progress through nucleation and growth, first of TiN and c-TiB0.5N0.5, followed by transformation of the B-rich precipitates to TiB2. The two-step process is interpreted as Guinier-Preston zone formation due to the incoherency between c-TiN and hexagonal TiB2. The nucleation was furthermore observed to be unclassical, with non-equilibrium compositions and extensive interfacial regions in the nuclei.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-84260 (URN)
Available from: 2012-10-03 Created: 2012-10-03 Last updated: 2016-08-31Bibliographically approved

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