Metal Matrix Composites Prepared by Powder Metallurgy Route

Ve všeobecnosti, poznatky o design slitin, jejich výrobě a výběru legujúcich prvků sú omezené na slitiny s jedním základním prvkem. Tento fakt ale výrazně limituje možnosti a volnost výběru prvků pro dosáhnuti speciálních vlastností a mikrostruktur. V poslední dekádě se ukázalo, že materiálová věda a inženýrství nejsou ještě zdaleka prozkoumané v důsledku objevu nové třídy materiálů nazvané vysoko entropické slitiny (HEA high entropy alloys). Jejich objev upoutal pozornost vědecké komunity. Základní koncept pro jejich design je, že namísto jednoho, nebo dvou základních prvků obsahují minimálně 5 prvků v podobných atomových koncentracích. V posledních letech se objevila skupina materiálů odvozená od HEA, nazvaná slitiny so střednou entropii (MEA medium entropy alloys). Na rozdíl od HEA ale obsahují 3, nebo 4 prvky. Táto práce je věnovaná studiu přípravy a charakterizaci HEA, MEA a jejich kompozitů s pomocí metod práškové metalurgie. V této práci byli dohromady zkoumány tři kompozice: AlCoCrFeNiTi0.5, Co1.5Ni1.5CrFeTi0.5 a CoCrNi, kompozity s kovovou matricí (MMC metal matrix composites) vyztužené částicemi B4C s CoCrNi jako matricí. Hloubková mikrostrukturní a mechanická analýza těchto materiálů byla provedena pomoví metod rastrovací a transmisní elektronové mikroskopie spojené s tahovými a ohybovými zkouškami. V průběhu celé studie se objevovaly problémy s kontaminací kyslíkem, co se projevilo vznikem značného množství oxidů v připravených materiálech. U Slitiny AlCoCrFeNiTi0.5 byla naměřena tvrdost přesahující 800 HV. Její houževnatost ale byla velice omezena. V její mikrostruktuře byly identifikovány částice in-situ TiC v důsledku přítomnosti organického, anti-aglomeračního činidla (metanolu) v mlecí misce. Tato reakce může být použita v budoucnu k přípravě MMC se záměrnou disperzí TiC. Na druhé straně, slitina CoCrNi ukázala vysoké hodnoty tažnosti (26%) a meze pevnosti přes 1000 MPa. Mikrostruktura obsahovala majoritní FCC fázi s BCC precipitáty. Tahle slitina byla z důvodu vysoké tažnosti zvolena pro přípravu kompozitu s výztuží B4C. V průběhu slinování ale došlo k reakci mezi přítomným Cr a B4C, které výsledkem byl Cr5B3 borid. Tento kompozit mel pevnost v tahu 1400 MP a extrémne jemnozrnnou strukturu. Celková tažnost ale klesla na 1.9 %. Slitina AlCoCrFeNiTi0.5, která mela strukturu složenou jen z FCC tuhého roztoku dosáhla nejlepší kombinaci mechanických vlastností s pevností přesahující 1300 MPa a dostatečnou tažností 4%. Prášková metalurgie se ukázala jako vhodná metoda pro přípravu HEA a MEA slitin a jejich kompozitů, s dobrou kombinací pevnosti a tažnosti. Tato metoda dovoluje měnit mikrostrukturní parametry připravených materiálů jednoduchou úpravou parametrů procesu.Conventionally, the alloy design, alloy production, and alloy selection are almost strictly confined to single element or one compound concept. Consequently, this alloy concept imposes a significant limit to the degrees of freedom in alloy’s composition and thus limits the development of special microstructure and properties. In the last decade, it has become particularly obvious that materials science and alloy engineering are still not fully explored due to an appearance of new class of alloys – usually called high entropy alloys (HEA). This exclusively new class of alloys caught significant scientific attention for the novelty of its approach to alloy design, as they do not contain a single base element, but rather at least 5 elements in very close atomic portions. In the recent years medium entropy alloys (MEA) appeared as a variant of HEAs with only three or four elements. The work is contributed to the research of feasibility of production of HEA and MEA alloys and composites by utilization of powder metallurgy (PM) manufacturing route, the combination of mechanical milling (MA) of elementary powders, followed by pressure or field assisted densification. Altogether three compositions have been studied: AlCoCrFeNiTi0.5, Co1.5Ni1.5CrFeTi0.5 and CoCrNi, as well as B4C metal matrix composite (MMC) with CoCrNi as matrix phase. Deep microstructural and mechanical analyses including transmission electron microscopy and tensile testing have been performed. During the whole study, the problems with the contamination of powders with oxygen have been observed, however the oxides formed relatively homogenous dispersion in all manufactured materials and they did not impair significant mechanical property reduction. AlCoCrFeNiTi0.5 exhibited relatively high hardness over 800 HV, but rather low ductility. The attempt has been made to improve the ductility with heat treatment procedure, but to no avail. The formation of in-situ TiC dispersion has been recorded, due to the utilization of carbon containing methanol as a process control agent during milling, that reacted with the present elemental Ti. In this manner metal matrix composite has been effectively produced. Additionally, the same procedure, the milling in the controlled amount of carbon containing medium, may be used also to produce other advanced composites with dispersion of in-situ formed TiC. On the other hand, CoCrNi alloy possessed very high tensile ductility (26%) and ultimate strength over 1000 MPa. Microstructure was composed of major FCC phase and BCC precipitates. The CoCrNi alloy has been due to the high ductility chosen as the best candidate for the subsequent production of metal matrix composites. The introduction of B4C resulted in the displacement reaction of Cr element with B4C, resulting in the formation of Cr5B3 boride phase. The composite possessed nano-grained microstructure and high tensile strength over 1400 MPa. However, the tensile ductility decreased to 1.9%. The AlCoCrFeNiTi0.5 alloy achieved the best combination of tensile ductility (4%) and remarkable strength over 1300 MPa, bearing pure FCC microstructure with extremely fine grain size. Therefore, the PM production route has proven to be a feasible way for the production of HEAs and MEAs, as well as HEA and MEA based metal matrix composites with remarkable combination of mechanical properties.

Nitrogen Interstitial Alloying of CoCrFeMnNi High Entropy Alloy through Reactive Powder Milling

The present work is focused on the synthesis of CoCrFeMnNi high entropy alloy (HEA) interstitially alloyed with nitrogen via powder metallurgy routes. Using a simple method, nitrogen was introduced to the HEA from the protective N2 gas atmosphere during mechanical alloying (MA) processing. The lattice parameter and amount of nitrogen in HEA were observed to be linearly proportional to the milling duration. The limited solubility of nitrogen in the main face centered cubic (FCC) phase resulted in the in-situ formation of nitrides and, accordingly, significant increase in the hardness values. It has been shown that fabrication of such nitrogen-doped HEA bulk materials can be conveniently achieved by a simple combination of MA + spark plasma sintering processes, without the need for adding nitrogen from other source

Influence of Ti on the Tensile Properties of the High-Strength Powder Metallurgy High Entropy Alloys

The focus of this study is the evaluation of the influence of Ti concentration on the tensile properties of powder metallurgy high entropy alloys. Three Ni1.5Co1.5CrFeTiX alloys with X = 0.3; 0.5 and 0.7 were produced by mechanical alloying and spark plasma sintering. Additional annealing heat treatment at 1100 °C was utilized to obtain homogenous single-phase face centered cubic (FCC) microstructures, with minor oxide inclusions. The results show that Ti increases the strength of the alloys by increasing the average atomic size misfit i.e., solid solution strengthening. An excellent combination of mechanical properties can be obtained by the proposed method. For instance, annealed Ni1,5Co1,5CrFeTi0.7 alloy possessed the ultimate tensile strength as high as ~1600 MPa at a tensile ductility of ~9%, despite the oxide contamination. The presented results may serve as a guideline for future alloy design of novel, inclusion-tolerant materials for sustainable metallurg

Tailoring a Refractory High Entropy Alloy by Powder Metallurgy Process Optimization

This paper reports the microstructural evolution and mechanical properties of a low-density Al0.3NbTa0.8Ti1.5V0.2Zr refractory high-entropy alloy (RHEA) prepared by means of a combination of mechanical alloying and spark plasma sintering (SPS). Prior to sintering, the morphology, chemical homogeneity and crystal structures of the powders were thoroughly investigated by varying the milling times to find optimal conditions for densification. The sintered bulk RHEAs were produced with diverse feedstock powder conditions. The microstructural development of the materials was analyzed in terms of phase composition and constitution, chemical homogeneity, and crystallographic properties. Hardness and elastic constants also were measured. The calculation of phase diagrams (CALPHAD) was performed to predict the phase changes in the alloy, and the results were compared with the experiments. Milling time seems to play a significant role in the contamination level of the sintered materials. Even though a protective atmosphere was used in the entire manufacturing process, carbide formation was detected in the sintered bulks as early as after 3 h of powder milling. Oxides were observed after 30 h due to wear of the high-carbon steel milling media and SPS consolidation. Ten hours of milling seems sufficient for achieving an optimal equilibrium between microstructural homogeneity and refinement, high hardness and minimal contamination.</p

Impact of interstitial elements on the stacking fault energy of an equiatomic CoCrNi medium entropy alloy: theory and experiments

We investigated the effects of interstitial N and C on the stacking fault energy (SFE) of an equiatomic CoCrNi medium entropy alloy. Results of computer modeling were compared to tensile deformation and electron microscopy data. Both N and C in solid solution increase the SFE of the face-centered cubic (FCC) alloy matrix at room temperature, with the former having a more significant effect by 240% for 0.5 at % N. Total energy calculations based on density functional theory (DFT) as well as thermodynamic modeling of the Gibbs free energy with the CALPHAD (CALculation of PHAse Diagrams) method reveal a stabilizing effect of N and C interstitials on the FCC lattice with respect to the hexagonal close-packed (HCP) CoCrNi-X (X: N, C) lattice. Scanning transmission electron microscopy (STEM) measurements of the width of dissociated 1/2 dislocations suggest that the SFE of CoCrNi increases from 22 to 42-44 mJ center dot m(-2) after doping the alloy with 0.5 at. % interstitial N. The higher SFE reduces the nucleation rates of twins, leading to an increase in the critical stress required to trigger deformation twinning, an effect which can be used to design load-dependent strain hardening response