Study of inter-atomic interactions in advanced materials with help of ab initio calculations

Pomocou COHP analýzy sme študovali chemickú väzbu v diboridoch prechodných kovov ako aj v zliatine Ni2MnGa. Elektrónová štruktúra študovaných materiálov bola vypočítaná použitím výpočtov z prvých princípov pomocou metódy PAW. V prípade diboridov tranzitných kovov z výsledkov vyplýva, že sila väzby bór-bór je silne závislá od transferu elektrónov na atómy bóru. Zvyšujúci sa počet valenčných elektrónov v kove spôsobuje destabilizáciu alfa štruktúry kvôli vzájomnej interakcii elektrónov prislúchajúcich jednému atómu (on-site interakcie) v blízkosti Fermiho hladiny. Pre zliatinu s tvarovou pamäťou Ni2MnGa bola použitá metóda DFT+ U upravujúca popis lokalizácie elektrónov. V prípade použitia parametra U na Ni dochádza k destabilizácii kubického austenitu a k stabilizácii tetragonálneho nemodulovaného martenzitu. Naopak, zvýšenie lokalizácie elektrónov mangánu martenzit destabilizuje. Analýza väzieb ukázala, že najsilnejšou väzbou je Ni-Ga s kovalentným charakterom. Zvýšená lokalizácia valenčných elektrónov Mn zvyšuje podiel kovalentnosti Mn-Ni väzby a kovový charakter Ni-Ni väzby. Vplyvom zvýšenej lokalizácie Ni elektrónov sa Mn-Ni väzba stáva viac kovovou.Chemical bonding in transition metal diborides and Ni2MnGa alloy was studied in terms of energy resolved COHP visualization tool. The electronic structure of studied systems was calculated using the first principles calculations with the help of projector augmented-wave method. Concerning transition metal diborides, we found dependence of the strongest boron-boron bond on the charge transfer from metal to boron atoms. The stability of diborides with the alpha structure decreases with higher number of metal valence electrons due to on-site contribution to the band energy near the Fermi level. Ni2MnGa shape memory alloy was treated by DFT+ U corrective method in order to describe localized electrons more accurately. The effect of U on Ni resides in destabilization of the cubic austenite and stabilization of the tetragonal NM martensite. On the contrary, U on Mn destabilizes martensite. The bond analysis shows that the strongest bond in the alloy is Ni-Ga with covalnet character. Increased localization of Mn valence electrons makes Mn-Ni bond more covalent and Ni-Ni bond more metallic. The localization of Ni electrons results in more metallic Mn-Ni bond.

Ab initio calculation of doping in Ni2MnGa alloy

Cieľom tejto práce je teoretické štúdium systému Ni-Mn-Ga, vykazujúceho efekt magnetickej tvarovej pamäti. Pri výpočtoch bola použitá metóda Exaktných Mufiin-Tin Orbitálov v kombinácii s aproximáciou koherentného potenciálu vrámci Korringa-Kohn-Rostoker formalizmu. Totálna energia bola spočítaná pomocou metódy úplnej nábojovej hustoty. Skúmaný bol vplyv dopovania zinkom alebo kadmiom na totálne energie pozdĺž tetragonálnej deformačnej dráhy a následne na teplotu martenzitickej premeny TM a Curieho teplotu TC. Taktiež boli skúmané nestechiometrické zliatiny prebytkom Mn na úkor Ga. Výsledky predikujú nárast TM po všetkých pozorovaných substitúciách v podmriežke Ga a pokles TM po substitúciách v podmriežke Mn. Curieho teplotu znižujú všetky študované substitúcie s výnimkou zmeny magnetického usporiadania v martensite nestechiometrickej zliatiny.The subject of this work is theoretical study of Ni-Mn-Ga system, known due to the magnetic shape memory effect. Calculations were performed using the Exact Muffin-Tin Orbitals method in combination with the Coherent Potential Approximation within the Korringa-Kohn-Rostoker formalism. The total energy was calculated by Full Charge Density method. Effects of Zn or Cd dopings on total energies along the tetragonal deformation path and consequently on martensite transformation temperature TM and Curie temperature TC were examined. Off-stoichiometric alloys with excess of Mn at the expose of Ga were studied as well. The increase in TM for all cases of doping in Ga sublattice and the decrease in TM for both cases of doping in Mn sublattice were predicted. Regarding TC, all types of doping should decrease Curie temperature with an exception of magnetic transition in the off-stoichiometric martensite.

On energetics of allotrope transformations in transition-metal diborides via plane-by-plane shearing

Transition metal diborides crystallise in the $\alpha$, $\gamma$, or $\omega$ type structure, in which pure transition metal layers alternate with pure boron layers stacked along the hexagonal [0001] axis. Here we view the prototypes as different stackings of the transition metal planes and suppose they can transform from one into another by a displacive transformation. Employing first-principles calculations, we simulate sliding of individual planes in the group IV-VII transition metal diborides along a transformation pathway connecting the $\alpha$, $\gamma$, and $\omega$ structure. Chemistry-related trends are predicted in terms of energetic and structural changes along a transformation pathway, together with the mechanical and dynamical stability of the different stackings. Our results suggest that MnB$_2$ and MoB$_2$ possess the overall lowest sliding barriers among the investigated TMB$_2$s. Furthermore, we discuss trends in strength and ductility indicators, including Young's modulus or Cauchy pressure, derived from elastic constants.Comment: 12 pages, 6 figures, accepted for publication in Vacuum, before proo

Ion-beam induced compositional and structural changes of Al-Cu-Co multilayer stacks

The present work deals with the investigation of ion-beam assisted annealing/mixing effects on compositional and structural changes in Al-Cu-Co multilayers. 800 nm thick Al64Cu20Co16 multilayers prepared by magnetron sputtering deposition, consisting of 28 successive single-metal Al-, Cu-, and Co-nanolayers were treated by thermal annealing at 300 °C, 400 °C, or 500 °C as well as ion irradiation by 30 MeV Cu5+ ions at fluences of 1x1013 to 5x1014 with an average flux of 2.38 × 1010 at.cm−2s−1. The samples were characterized with SEM, EDX, XRD, and TEM including HAADF. In contrast to the original multilayer, the treated samples were found to consist of two types of alternating nanolayers. A wider coarse-grained structurally and chemically homogeneous single-phase nanolayer formed by Al2Cu, and a narrow fine-grained two-phase nanolayer, which has a heterogeneous composite structure in which the central Co sublayer (being a residue of the original single-metal Co nanolayer) is surrounded from both sides with Al-Co sublayers, consisting of Al9Co2. This Co sublayer is considered to be a diffusion blocker for Al and Cu as well as hindering the movement of borders between particular nanolayers. The formation of a ternary phase in the investigated samples was not confirmed in any of the samples

Similarity between Effects of Laves Phase and M6C in Alloy Steels

The aim of this work is to summarize the experimental result obtained within the last two decades about the effects of Laves phase and M6C during long-term thermal exposures of alloy steels. The intergranular Laves phase (12CrMoV steel) and/or M6C (3CrMoV steel) particles were found to evoke the anomaly in the kinetic dependence of phosphorus grain boundary concentration. In comparison to other phases usually present in Cr-Mo alloy steels, Laves phase and M6C precipitate after longer periods of annealing and dissolve non-metallic elements such as phosphorus or silicon. A partitioning of originally segregated phosphorus between the matrix and the newly precipitated Laves phase and/or M6C particles led to the decrease in the phosphorus grain boundary concentration

Influence of Secondary Phase Precipitation on Resistance to Intergranular Corrosion of AiSi 316l Austenitic Stainless Steel

The AISI 316L steel after cold working of 40% and subsequent annealing at 750°C for 1, 2, 5, 10, 50, or 100 h was investigated. For the microstructure characterization the light microscopy and the transmission electron microscopy were used. To determine the sensitivity to intergranular corrosion the test was performed according to ASTM A 262, practice A. The transition between non-sensitised and sensitised states was found to be between 1 and 2 h of annealing. Sigma, laves and chi phases were identified in all the analyzed conditions. M23C6 was found to start to precipitate between 5 and 10 h of annealing. Sigma, chi, and M23C6 precipitated mainly along the grain boundaries. Laves precipitated mainly inside the grains, and after 50 h of annealing also intergranularly. Time dependent changes in the average metal composition of particular phases were considered as negligible