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The wear resistance of boron-modified supermartensitic stainless steel coatings produced by high-velocity oxygen fuel (HVOF) was investigated through pin-on-disk measurements. It was shown that addition of boron leads to the formation of an interconnected and rigid boride network delimiting the grain boundaries of the martensitic matrix. A very refined structure was formed as result of the high cooling rates imposed to the molten alloy during the HVOF process. The specific wear rates of the HVOF coatings were about tenfold lower than the boron-free supermartensitic stainless steel, lying in the order of 10−5 mm3/N m. The refined boride skeleton along the HVOF coating was found to be effective to reduce the materials’ removal from the exposed softer martensitic matrix. While the supermartensitic stainless steel master alloy and the mild steel substrate displayed severe adhesive wear, the HVOF coatings exhibited mild delamination wear at low sliding velocities (10 and 20 cm/s) and abrasive wear at the highest tested velocity (40 cm/s). The studied boron-modified supermartensitic HVOF coatings are an interesting approach to protect the surface of inexpensive steel substrates against wear.

An in-depth analysis of the effect of boron addition on the microstructure of the equiatomic AlCoCrFeNi High Entropy Alloy (HEA) was performed. Alloys with nominal compositions AlCoCrFeNiB0.1 and AlCoCrFeNi were produced and analyzed by multi-scale characterization techniques, including X-ray diffraction, scanning and transmission electron microscopy coupled with TEM-based orientation mapping technique. CALPHAD simulation was carried out to understand the solidification sequence and the phase stability of the studied alloys. The equiatomic AlCoCrFeNi alloy forms a mixture of an Al-Ni rich B2 phase with a Fe-Cr rich body centered cubic (BCC) phase; small face centered cubic (FCC) islands were also observed. The boron addition leads to the formation of needle-like Cr-rich borides with an orthorhombic structure. Moreover, this addition changes considerably the solidification sequence in later stages of the solidification process, resulting in a more complex microstructure.

FeCrMnCoSi coating (so-called CaviTec alloy) is recognized as an efficient protective measure to extend the service-life of steel components subjected to severe cavitation erosion. Besides this requirement, many applications also demand coatings with proper corrosion and wear resistances. The aim of this study is to evaluate the pitting corrosion and the sliding wear resistances of CaviTec coatings produced by high-velocity oxygen fuel (HVOF) and deposited onto a 304 stainless steel (SS). The corrosion performances in simulated seawater indicated that these coatings exhibit satisfactory corrosion resistance with regions around the inter-splats representing the preferential weak links sites for pitting corrosion initiation. CaviTec coating wear is characterized by mild delamination followed by severe abrasive wear once the hard-martensitic debris are added in the tribosystem due to the transformation induced plasticity (TRIP) effect. Corrosion and wear results point out that the CaviTec coatings, originally developed to possess high cavitation erosion resistance, also present satisfactory corrosion resistance in seawater-like medium and interesting dry sliding wear performance, which can extend their application domain.

Pseudo-high entropy (PHE) amorphous alloys have emerged as novel metallic materials. Some Fe-containing PHE amorphous alloys display the unique characteristic of maintaining a clustered glassy structure in a wide temperature range, and eventually crystallize multi-principal element (MPE) phases whose composition is close to the parental alloy composition. Therefore, these PHE amorphous alloys promise to surpass the trade-off between crystallization and corrosion resistance typical of most bulk metallic glasses. This work investigates the corrosion resistance in chloride media of (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)100−xBx (x = 8, 10, 12) alloys produced by melt-spinning. The B-richest composition, (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)88B12, ensured fully amorphous ribbons, while MPE nanocrystals were formed within the amorphous (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)90B10 and (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)92B8 ribbons. All alloys were corrosion-resistant in acidic (pH 3) and alkaline (pH 10) chloride-rich electrolyte (35 g L−1 NaCl) and in a hypersaline medium (250 g L−1 NaCl, pH 3), as verified from potentiodynamic polarization and electrochemical impedance spectroscopy measurements. From x-ray photoelectron spectroscopy, the formation of a nanometric-thick film composed of Fe-, Co-, Ni-, Cr-, and Mo- compounds on the alloys' surface was observed, responsible for granting the corrosion resistance of all alloys. Although containing crystals, the B-poorest alloy, (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)92B8, presented comparable and even superior corrosion resistance than the fully amorphous B-richest alloy, (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)88B12. The maintenance of the corrosion resistance of the (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)90B10 and (Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)92B8 alloys in the presence of crystals were ascribed to the reduced elemental partition upon crystallization of MPE phases. The excellent corrosion resistance nevertheless vanished if excessive crystallization occurs, forming borides. These findings open new prospects for overcoming the corrosion-wear resistance paradigm of amorphous/crystalline alloys, essential to design materials and coatings to endure harsh environments.

The behaviour of the martensitic phase transformation of a Cu-Al-Ni-Mn shape memory alloy was studied for as-atomized and heat-treated powders. X-ray diffraction, microscopy techniques and thermodynamic calculations were used to understand the different transformation behaviour observed during differential scanning calorimetry (DSC) analysis. Two overlapped transformation peaks were observed in the DSC curves for the as-atomized powder. After annealing, the peaks progressively became only single peak when the annealing temperature and time were increased. No difference in phase formation and microstructure was observed by X-ray diffraction and scanning electron microscopy when compared as-atomized and annealed powders, although transmission electron microscopy analyses showed that the as-cast powders had more dislocations trapped in the microstructure than the annealed samples. Considering the experimental results and thermodynamic considerations, it was concluded that the smooth double peak effect in the as-atomized powders occurred due to a different state of internal stresses and elastic energy accumulation during forward transformation. The absence of this effect after heat treatment shows that the internal stresses and defects were annihilated after annealing, changing the elastic energy accumulation and the transformation behaviour. Understanding the martensitic transformation on Cu-Al-Ni-Mn powders is important considering the potential use of powder metallurgy processing route.

Wear and corrosion resistant amorphous/nanocrystalline Fe-Cr-Nb-B coatings have been successfully synthesized by high velocity oxygen fuel in previous works. These coatings show excellent wear resistance and superior corrosion resistance. However, the phase evolution during cooling of the new alloys in the Fe-Cr-Nb-B system is not well understood. In addition, commercial thermodynamic databases for Fe-based alloys do not fully describe the system at the composition ranges of interest. In the present work, the phase evolution of as-melted Fe 51 Cr 10 Nb 20 B 19 alloy was investigated by combining detailed microstructural characterization with thermodynamic evaluation using a database developed for the Fe-Nb-B system. The solidification path starts with the formation of (Fe,Cr,Nb) 3 B 2 diboride phase, followed by the formation of austenite at lower temperature. On further cooling, the remaining liquid transforms eutectically to (Fe,Cr)NbB boride and austenite. In the solid-state region, the austenite transform allotropically to ferrite. At even lower temperature, there exists a peritectoid-like transformation, where the (Fe,Cr)NbB boride nucleates both at ferrite grain boundaries and around the existing (Fe,Cr,Nb) 3 B 2 diboride. Thermodynamic calculations showed good agreement with experimental observations, opening new possibilities to guide future alloy development in the Fe-Cr-Nb-B quaternary system.

The influence of Cr addition in a rapidly solidified Al-Ni-Co alloy was investigated. Melt spun samples of atomic composition Al71Ni20Co9, Al72Ni19Co7Cr2 and Al72Ni20Co5Cr3 were studied by X-ray diffraction and transmission electron microscopy. Aiming to develop quasicrystalline compositions enriched in corrosion resistant elements such as Cr and Ni this work presents, for the first time, the effect of Cr addition on the quasicrystalline phase formation of a high-Ni Al-Ni-Co rapidly solidified alloy chosen to be within the range of formation of the decagonal quasicrystalline phase observed in this ternary system. The composition of the quaternary alloys was chosen by reducing the Co content in favor of Cr on the ternary alloy and keeping the average valence electron per atom (e/a) around 1.86. The phase constitution of the ternary alloy consisted of the decagonal phase along with two intermetallic phases, Al3Ni and Al3Ni2. The addition of Cr resulted in the formation of a second quasicrystalline decagonal phase, rich in Cr. This was due to the low Cr solubility on the ternary Al-Ni-Co decagonal and intermetallic phases, which rejected Cr and resulted on the formation of the Cr-rich quasicrystal.

A structural, mechanical and thermal characterization of an Al-Co-Fe-Cr coating alloy was performed. An atomized powder with atomic composition of Al 71 Co 13 Fe 8 Cr 8 was thermally sprayed by high velocity oxygen fuel (HVOF) on a steel substrate. X-ray diffraction, scanning and transmission electron microscopy and differential scanning calorimetry were used to characterize the atomized powder and the sprayed coating. Vickers microhardness and pin-on- plate wear test were carried out for mechanical and tribological characterization and an infrared camera was used to evaluate the insulation capacity of the coating material. The results show that both the atomized powder and the coating material were composed predominantly by a quaternary extension of the hexagonal Al 5 Co 2 phase and by the monoclinic Al 13 Co 4 . Both phases are quasicrystalline approximants of a decagonal Al-Co quasicrystal. The coating samples presented high values of micro-hardness, close to 500 HV and substantially low friction coefficient values, around 0.05. The coatings were good thermal insulators, decreasing by 30% the surface temperature of a sample exposed to a hot plate in comparison with the carbon steel substrate.

Recently a Fe 60 Cr 8 Nb 8 B 24 quaternary amorphous/nanocrystalline composite coating has been successfully synthesized by high velocity oxygen fuel in our group. The composite coating shows excellent wear and corrosion resistance. In order to understand the phase evolution of the quaternary alloy during cooling and interpret its good glass forming ability, the stable phases in the as-melted ingot of the same composition were studied by X-Ray diffraction, scanning electron microscopy, transmission electron microscopy and differential scanning calorimetry. Thermodynamic calculation was performed based on a database compiled from literature. The calculated results show good agreement with the microstructural observation. It was found that Fe 60 Cr 8 Nb 8 B 24 alloy lies very close to the eutectic point of the system, which is related to its high glass forming ability. The thermodynamic calculation could provide insightful understanding and guidance for the future amorphous composition designing in Fe-Cr-Nb-B quaternary system.

The conflicting role of crystalline phase on the corrosion and wear resistance of the glass former Fe66Cr10Nb5B19 alloy was investigated. Amorphous to crystalline structures were produced by amorphous ribbons annealing and solidification of the liquid into a wedge-shaped copper mold. Amorphous and amorphous/nanocrystalline microstructures displayed good balance of properties. Their corrosion resistance remained elevated since α-(Fe,Cr) and (Fe,Cr)2B crystals were non-percolated within the corrosion-resistant amorphous matrix. Wear resistance was still high because (Fe,Cr)2B is even harder than the amorphous matrix. Crystalline microstructures were resistant against wear thanks to the large fraction of (Fe,Cr)2B and (Fe,Cr)NbB, both effective to protect the softer α-(Fe,Cr) matrix. Their corrosion resistance, however, was severely compromised, given the elemental partitioning to form crystals, with the interfaces more prone to corrode. While amorphous and amorphous/nanocrystalline microstructures presented the best-combined resistance to corrosion and wear, the crystalline microstructures are interesting for load-bearing applications where high corrosion resistance is not required.

In this work, the effect of Si additions on the glass-forming ability (GFA) and the mechanical behaviour of a Ti42.5Cu42.5Ni7.5Zr7.5 alloy is investigated. An optimum GFA occurs for addition of 0.5 at% Si and it is explained based on a balance between two factors: an increased thermal stability of the supercooled liquid and the detrimental effect of Ti5Si3 on vitrification. On rapid cooling, composites consisting mainly of the cubic B2 phase and glass can form. Their plasticity increases with increasing Si additions without sacrificing their high yield strength. A characteristic core–shell microstructure is formed in the rod with 2 at% Si, for which the combination of an amorphous outer surface and a refined dendritic structure in the centre gives rise to a composite with enhanced mechanical properties.

In this work, the corrosion behavior of amorphous and partially crystallized Fe68Cr8Mo4Nb4B16 alloys has been studied. Fully amorphous ribbons were prepared by melt spinning and then partially and fully crystallized at different heat treatment temperatures. The corrosion behavior was evaluated in chloride-rich media at different pHs, ranging from acidic to alkaline. An exceptionally high corrosion resistance was observed for the new Fe68Cr8Mo4Nb4B16 amorphous alloy in the proposed media and pHs. The amorphous phase containing corrosion-resistant alloying elements such as chromium and molybdenum led to the formation of a highly stable passivating film, which coated and protected the active exposed metal surface. Partially crystallized samples heated up to 700 °C still grant the formation of a corrosion-resistant passivating layer. The presence of such a layer was correlated to the non-percolation of crystals embedded into the corrosion-resistant amorphous matrix. The corrosion resistance of fully crystalline annealed ribbons and as-cast ingots did not present the similar superior corrosion performance. This behavior was assigned to element partitioning throughout the crystallization, particularly chromium, which led to a non-homogeneous structure that preferentially triggered and held pitting corrosion along with the percolated crystalline material. These results indicate that the Fe68Cr8Mo4Nb4B16 alloy is a candidate for corrosion resistant coating where the suppression of crystallization is unavoidable.

High-entropy (Fe0.25Co0.25Ni0.25Cr0.125Mo0.0625Nb0.0625)100‒xBx amorphous alloys are formed with low (8–14 at%) boron contents by melt spinning. With increasing boron, the broad halo in X-ray diffraction shifts to indicate a decreasing average spacing of nearest-neighbor atoms. The crystallization onset temperature and the Vickers hardness increase with boron content. The glass transition is observed even for a low-boron (13 at%) alloy. The 8–11 at% B alloys crystallize in stages: [am] → [am’ + bcc] → [am″ + bcc + fcc] → [bcc + fcc + borides]. The bcc precipitates, diameter ∼10 nm enriched in (Fe,Co) and the fcc precipitates, diameter ∼15 nm enriched in (Ni,Fe), are stable on annealing over a wide range (900–1060 K) below the temperature at which borides form. The bcc phase shows no internal defects, while the fcc phase has defects such as twin boundaries. The microhardness (Hv) of the [am″ + bcc + fcc] nanostructure reaches a high maximum of 1460–1560 kgf‧mm−2, before decreasing rapidly when the formation of borides marks the disappearance of the residual amorphous phase. The high thermal stability of the three-phase nanostructure is attributed to the residual amorphous phase enriched in B, Cr, Mo and Nb. These low-boron metastable alloys with novel three-phase nanostructures are attractive as potential amorphous coatings or ultrahard structural alloys with high thermal stability.

This work reports on the degradation of two (Zn-poor and Zn-rich) Mg-Zn-Ca crystalline alloys produced by mold casting yielding different kinds of microstructures with several scales. The dependence of corrosion properties and hydrogen evolution with alloy compositions, sizes and kinds of microstructure was exhaustively analyzed. The results were compared with amorphous alloys of same compositions. Zn-rich composition with average grain sizes of less than 500 nm presented marginal and an acceptable level of hydrogen, which was lower than for larger grains or Zn-poor composition. This behavior was explained by the reduction of the intrinsic metallic surface reactivity and the higher stability of the oxide film, which reduce the corrosion rate and, consequently, the hydrogen evolution. Mg-Zn-Ca crystalline alloys with Zn-alloying threshold and homogeneous grain size (

In this work, we present a wear-resistant coating fabricated by non-vacuum electron beam cladding of Fe62Cr10Nb12B16 at.% powder on a mild steel substrate. The protective coating was 1.3 mm thick, dense, and exhibited an α-(Fe,Cr) matrix reinforced by a significant fraction of hard borides formed upon solidification. Micrometric and nanometric borides homogeneously dispersed within the matrix were formed due to the homogeneous melting and the relatively fast cooling to suppress the excessive phase growth. An intimate metallurgically bonded interface between the coating and substrate was characterized by low compositional dilution and a fine eutectic-like transition zone microstructure anchoring the dissimilar materials. The coatings displayed a higher wear resistance compared to the mild steel substrate, showing specific wear rates, κ, about one order of magnitude lower (10−5 against 10−4 mm3/N.m, respectively). The abrasive wear mechanism was dominant for the coating sample when tested at low sliding velocity, 10 cm/s, due to the detachment of hard borides from the surface and their incorporation into the tribosystem. The adhesive wear mechanism was found to be dominant at higher sliding velocities of 20 and 40 cm/s. Dry sand/rubber wheel testing revealed the higher resistance of the coating against abrasive wear compared to the mild steel substrate. Regardless of the wear mechanism, the Fe62Cr10Nb12B16 at.% coatings showed a superior sliding and abrasive wear resistance and represented an interesting protective measure to extend the service of inexpensive mild steel components.

Cu–45Zr–8Al and Cu–44.1Zr–7.8Al–2Y metallic glass ribbons were prepared by melt spinning and heat treated at two different temperatures followed by microstructural characterization by SEM and TEM. The compositions were selected to better understand the effect that oxygen has in the sequence and morphology of the phases formed during devitrification. A novel microstructure consisting of the Heusler Cu 2 ZrAl phase precipitated inside a B2–CuZr matrix that has shape memory properties was produced. It is proposed that this novel microstructure may be used to prepare samples with improved shape memory responses. The known cube–cube relationship between the Heusler and B2 phases also provides direct evidence about the orientation relationship between the martensite and the parent B2 austenite and the results are in contrast to what is reported in the literature. The results also confirm that oxygen dissolved in these alloys leads to the formation of the B2–CuZr phase at lower temperatures than comparable low oxygen alloys.

The crystallization behavior of Cu–Zr–Al alloys with different contents of oxygen and yttrium was studied. Three compositions were chosen based on the good glass former Cu–45Zr–8Al with varying Y contents (0, 0.3 and 2%) added to getter the oxygen from the glass. Melt spun ribbons were prepared and their crystallization behavior was analyzed by differential scanning calorimetry (DSC). Heat treatments were performed at selected temperatures based on the DSC data and the phases formed were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results revealed that oxygen has a strong influence on the crystallization behavior, it changes the mode and the phases formed and results in the formation of a metastable crystalline phase prior to the formation of the stable phases. The Y was found to have a more subtle effect: it lowers the incubation time for crystallization and promotes heterogeneous nucleation of Cu10Zr7 and, therefore, adding Y to these alloys has this important drawback that is reported for the first time here. The mechanisms by which each of these elements acts are suggested. Finally the formation of defects in the Cu10Zr7 phase is reported.

In this study the Fe43.2Co28.8B19.2Si4.8Nb4 (at.%) alloy was processed by spray forming in an industrial facility with the aim of investigating the formation of amorphous phases. The thicker layers (5–15 mm) presented partial/fully crystalline microstructure with onset of crystallization of the amorphous phase at T x = 595 °C. On the other hand, thinner layers (below 2.5 mm) presented fully amorphous structure, and glassy behaviour with glass transition (T g ) at 555 °C. The thermal stability and the crystallization kinetics of the alloy were studied using the isothermal DSC curves, measured at different heating rates and temperatures. Despite its good glass-forming ability (GFA) and high stability against crystallizations, its incubation time for crystallization is almost zero. In order to rule-out the complete crystallization mechanism, in situ temperature resolved studies using TEM were done. In addition, the amorphous part of the deposit was heat treated at various temperatures/times and the results were compared with the in situ crystallization behavior observed by TEM.

Bulk consolidated samples of 2 Mg–Fe were produced by hot extrusion and by hot extrusion followed by cold rolling. The starting 2 Mg–Fe mixture was obtained by high-energy ball milling. The cold-rolled samples, which presented a favorable (0 0 2) texture in Mg, absorbed 5.23 wt.% H2, almost the full capacity of Mg2FeH6, without any incubation time. This level of hydrogen absorption capacity was higher than the ones observed for the milled powders or the extruded samples. The hydrogen desorption temperatures were very close for all types of samples. The good results observed in the hot-extruded plus cold-rolled sample were explained by the smaller grain sizes, along with a favorable texture and the catalytic effect of residual Fe.

Commercial Mg was processed by two combined processes: ECAP and cold rolling. Samples were first processed by ECAP for four passes using route Bc, at 300 °C and ram speeds of 3 and 25 mm/min. The ECAPed samples were cold-rolled in several passes. The cold rolled samples, which presented a favorable (0 0 2) texture, presented faster hydrogen absorption kinetic than the just ECAPed samples. No significant changes of desorption temperatures were found. The good results observed in the ECAPed plus cold rolled samples were explained by the acquired preferred orientation and by the increase of defects after cold rolling.

The thermal crystallization of Al-based metallic glasses can be described in association with the topological instability λ criterion. In the present work, we report on the crystallization behavior and glass forming ability of Al-rich, Al–Ni–Sm alloys, designed with compositions corresponding to the same topological instability condition of λ ≈ 0.1. Amorphous melt-spun alloys were prepared with the following compositions, varying the ratio of Ni and Sm elements: Al 87.5 Ni 4 Sm 8.5 , Al 83.5 Ni 10 Sm 6.5 , Al 80.5 Ni 14.5 Sm 5 and Al 76.5 Ni 20.5 Sm 3 . The glass forming ability of each alloy composition was evaluated based on the thermal parameters obtained from DSC runs and on X-ray diffraction patterns. Better glass forming ability was observed in compositions whose Sm content was increased and Ni content reduced. Thermal crystallization of the alloys with low Sm content showed only one crystallization peak and no glass transition event. In alloys with higher rare-earth content, a glass transition event was clearly detected before the crystallization event. The results are interpreted considering the different types and proportions of Sm–Al and Ni–Al clusters that can be formed in the alloys along the λ ≈ 0.1 line. They also emphasize the relevance of these different types of clusters in the amorphous phase in defining the stability of the glass and the types of thermal crystallization.

Fe–Si alloys have excellent soft magnetic properties, especially around 12 at.% Si. However, their industrial applications are limited because they lack the ductility required in rolling operations for the fabrication of thin sheets, thus leading to cracking. The brittleness of high silicon alloys is caused by order–disorder reactions at low temperatures. This work involved an analysis of the effect of heat treatment on the crystalline structure of thin sheets of Fe–5 wt%Si alloy obtained in a two-step fabrication route: (1) spray forming of Fe–3.5%Si + 2.0%Sip composite and (2) rolling and heat treatment of the composite to dissolve the silicon and homogenize its content across the thickness of sheet samples. Structural and microstructural analyses indicated the success in fabricating thin sheets of Fe–5 wt%Si alloys with such strategy. The presence of the ordered B2 phase had an important effect on the texture development and therefore on the magnetic properties of these alloys.

In this work, a criterion considering the topological instability ( λ ) and the differences in the electronegativity of the constituent elements (Δ e ) was applied to the Al–La and Al–Ni–La systems in order to predict the best glass-forming compositions. The results were compared with literature data and with our own experimental data for the Al–La–Ni system. The alloy described in the literature as the best glass former in the Al–La system is located near the point with local maximum for the λ ·Δ e criterion. A good agreement was found between the predictions of the λ ·Δ e criterion and literature data in the Al–La–Ni system, with the region of the best glass-forming ability (GFA) and largest supercooled liquid region (Δ T x ) coinciding with the best compositional region for amorphization indicated by the λ ·Δ e criterion. Four new glassy compositions were found in the Al–La–Ni system, with the best predicted composition presenting the best glass-forming ability observed so far for this system. Although the λ ·Δ e criterion needs further refinements for completely describe the glass-forming ability in the Al–La and Al–La–Ni systems, the results demonstrated that this criterion is a good tool to predict new glass-forming compositions.

Fe–Si alloys are widely used for magnetic applications. However, it is very difficult to process Fe–Si with a silicon content exceeding 3.5 wt.%Si (upper limit for products commercially available by the I/M route) due to the alloy's low ductility, which is attributed mainly to the formation of B2 and DO3 ordered phases that embrittle the material. To overcome this obstacle, the main focus of this work was to produce thin sheets of Fe–5 wt.%Si alloy in two steps: (1) as a Fe–3.5%Si + 3%Sip (Si particles) composite, using spray forming, and (2) rolling and heat treating (HT) the composite to dissolve the silicon and homogenize its content throughout the thickness of the sheet. To this end, 3 wt.%Sip were co-injected into the main stream of the Fe–3.5 wt.%Si spray, followed by hot-rolling of the billet at 850 °C to obtain 0.45 mm gauge thin sheets. The final material was heat-treated at 780/510 °C for 8 h or at 1250 °C for 1 h and then air cooled. The grain orientation was analyzed by EBSD and the distribution of iron, silicon and impurities was identified by X-ray dot mapping. The heat treatment caused diffusion and dissolution of the silicon particles and grain growth. However, the final silicon content was strongly dependent on the atmosphere of the heat treatment furnace. In the absence of oxygen, the silicon content reached 4.9 wt.% distributed homogeneously throughout the thickness of the composite. In the presence of oxygen, the silicon diffused to the surface and only 3.5 wt.% remained in the matrix.

The present paper evaluates the corrosion resistance of four new amorphous Fe-Cr-based alloys containing Mo or Nb, as well as their thermal stability and the effect of their partial crystallization. Ribbons of Fe 68 B 20 Cr 12 , Fe 67.7 B 20 Cr 12 Mo 0,3 , Fe 67.7 B 20 Cr 12 Nb 0,3 and Fe 67.7 B 20 Cr 12 Nb 0,15 Mo 0,15 alloys were processed by the melt-spinning technique. The crystallization process of the four compositions occurs in a single-stage step with the simultaneous precipitation of fcc-Fe and Fe 3.5 B phases . The addition of Nb and/or Mo leads to an increase in the crystallization temperature, indicating that these elements stabilize the amorphous phase. The results also indicate that the alloy containing both Nb and Mo presented greater uniform corrosion resistance than the alloy containing either one or the other of these elements in NaCl and H 2 SO 4 solution.

article i nfo Article history: Received 8 December 2009 An investigation was made into the thermal stability and mechanical behavior under nanoindentation of a new glassy alloy with composition Ni50Nb28Zr22, produced in the form of melt-spun ribbons and copper mold-cast wedges. The alloy composition was designed based on the lambda criterion combined with the electronegativity difference among the elements. X-ray diffraction and scanning electron microscopy confirmed that the ribbons and wedges (up to 200 μm in thickness) are amorphous. The thermal properties of these samples were evaluated by differential scanning calorimetry (DSC). Nanoindentation revealed that the hardness of this alloy, around 10 GPa, is among the highest reported for metallic glasses. Remarkably, the cast wedge exhibits greater hardness and higher elastic modulus than the ribbon. This correlates with the larger amount of frozen-in free volume in the ribbons than in the cast wedges, as evidenced by DSC. In addition, finite element simulations of nanoindentation curves were performed. The Mohr-Coulomb yield criterion allows for better adjustment of the experimental data than the pressure-independent Tresca yield criterion. The simulations also reveal that the cohesive stress in the ribbons is lower than in the wedges, which explains the difference in hardness and Young's modulus between the two samples.

In this study, the effect of the microstructural characteristics on the mechanical properties of rapidly solidified A359-type alloy was analyzed. As a result of the rapid solidification processing by melt-spinning, fine equiaxed cells grains with sizes in the range of 0.4–0.7 μm were observed in the ribbon. Heat treatment of the as melt-spun ribbon showed a growth of the nanosized Si particles from 19 nm to 80 nm (200 °C/12 h) and to 1.72 μm (450 °C/12 h). The improvement in hardness and tensile properties are related to supersaturated α-Al solid solution and to the structural refinement. The decrease in hardness and in the tensile properties after thermal ageing is attributed to Si precipitation and subsequent growth of Si particles. The as melt-spun and after heat treated at 200 °C ribbons exhibited a brittle fracture different of the after heat treated at 450 °C ribbon which showed a ductile fracture surface.

In the present work, an Al–Fe–Cr–Ti alloy with adequate composition to form quasicrystalline phases has been surface remelted using laser processing techniques. The surface of spray formed Al91Fe4Cr3Ti2 bulk samples was remelted using a 2 kW CW Nd:YAG laser. Two different laser beam powers were applied with the goal of studying its influence in the quasicrystalline phase formation in the remelted coating. After laser treatment, the samples were characterized by X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (FEG-SEM). The formation of quasicrystalline phases was observed in the X-ray diffractograms and their transformations were verified in DSC analyses. A greater formation of quasicrystalline phase was verified in the coating produced with smaller laser beam power, i.e. higher cooling rate, and its morphology was more close to the sphere. The results indicate the possibility of producing low density coatings containing quasicrystalline phases by laser remelting of spray formed materials.

Aluminum matrix composites reinforced with Al–Ni intermetallic compounds and Al 2 O 3 were obtained by hot pressing of high-energy milled powders. Using the reaction between Al and NiO and aiming to preserve part of the Al content after completing the reaction by increasing the relative amount of Al, composites containing Al 2 O 3 and Al–Ni intermetallic compounds were produced. These composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Depending on the Al/NiO molar ratio, the reaction can be activated either during milling or during subsequent hot pressing. Hence, two different processing routes can be used to produce such composites. Starting from powder mixtures with an Al/NiO molar ratio of 15/3, the reaction took place during milling, forming Al 3 Ni and Al 3 Ni 2 plus Al 2 O 3 reinforced Al composite powder, which was consolidated by hot pressing. An Al/NiO molar ratio of 20/3 prevented the reaction from occurring during milling, but enabled it to occur during subsequent hot pressing, forming the same reinforcement phases. The reactive-milled composite is harder and presents higher porosity than the reactive-sintered ones, after consolidation by hot pressing under the same parameters. In the latter route, the longer the milling time prior to hot pressing, the smaller the size of the reinforcement phases.

In the present work, the glass forming ability (GFA) and its compositional dependence on Al-Ni-Ce system alloys were investigated as a function of several thermal parameters. Rapidly quenched Al 85 Ni 15-x Cex (X=4,5,6,7,10), Al 90 Ni 5 Ce 5 , Al 89 Ni 2.4 Ce 8.6 , Al 80 Ni 15.6 Ce 4.4 and Al 78 Ni 18.5 Ce 3.5 amorphous ribbons were produced by melt-spinning and the structural transformation during heating was studied using a combination of X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The results showed that the GFA and the thermal stability in the Al-rich corner of Al-Ni-Ce system alloys were enhanced by increasing the solute content and specifically the Ce content. © 2008 Elsevier B.V. All rights reserved.

Amorphous alloys present exceptional values of mechanical strength but lack any significant plasticity at room temperature. Deformation of amorphous alloys occurs in shear transformation zones that connect to form shear bands, which are easier to deform than the surrounding matrix, thus facilitating further deformation in the same location of the specimen. However, the presence of particles dispersed in the amorphous matrix can modify such strain softening behavior, resulting in real plastic deformation before fracture. Also, depending on the type of particles and how they are introduced, they can modify the crystallization behavior of the amorphous matrix by acting as heterogeneous nucleation sites. In this context, this paper reports on the effects of the addition of SiC particles on the crystallization of Al 84 Ni 8 Co 4 Y 3 Zr 1 amorphous ribbons. Pre-alloyed ingots with and without added SiC particles were melt-quenched into amorphous ribbons by the single-roller melt-spinning technique and then selectively and partially crystallized at the first and second crystallization temperatures, as determined by differential scanning calorimetry. Primary crystallization of nanometric-sized fcc-Al crystals was found to occur in both ribbons (with and without added SiC), confirming that crystallization reactions were not altered by the ceramic particles. Aluminum carbide (Al 4 C 3 ) crystals resulting from high-temperature liquid metal/SiC reactions were observed as coatings on the SiC particles and as isolated particles dispersed in the amorphous solid matrix. In both cases, the Al 4 C 3 particles also did not change the crystallization behavior of the amorphous Al 84 Ni 8 Co 4 Y 3 Zr 1 matrix, since no heterogeneous nucleation of fcc-Al crystals was observed.

A thermodynamic approach to predict bulk glass-forming compositions in binary metallic systems was recently proposed. In this approach, the parameter γ * = Δ H amor /(Δ H inter − Δ H amor ) indicates the glass-forming ability (GFA) from the standpoint of the driving force to form different competing phases, and Δ H amor and Δ H inter are the enthalpies for glass and intermetallic formation, respectively. Good glass-forming compositions should have a large negative enthalpy for glass formation and a very small difference for intermetallic formation, thus making the glassy phase easily reachable even under low cooling rates. The γ * parameter showed a good correlation with GFA experimental data in the Ni–Nb binary system. In this work, a simple extension of the γ * parameter is applied in the ternary Al–Ni–Y system. The calculated γ * isocontours in the ternary diagram are compared with experimental results of glass formation in that system. Despite some misfitting, the best glass formers are found quite close to the highest γ * values, leading to the conclusion that this thermodynamic approach can be extended to ternary systems, serving as a useful tool for the development of new glass-forming compositions. Finally the thermodynamic approach is compared with the topological instability criteria used to predict the thermal behavior of glassy Al alloys.

The microstructure and the tensile properties of an spray co-deposited Al-8.9 wt.% Si-3.2 wt.% Cu-0.9 wt.% Fe + (Al-3 wt.% Mn-4 wt.% Si)p composite was investigated after extrusion and heat treatment. The composition of the AlMnSi p alloy was selected aiming to improve the formation of α-Al(Fe,Mn)Si instead of β-Al(Fe,Mn)Si intermetallic. The spray formed deposits were extruded at 623 K and heat treated to peak aged (T6) condition. Room temperature tensile tests of the spray formed and extruded/heat treated alloy showed significant increase of elongation to fracture when compared with the values observed for the as-spray formed deposits, >10% and

In the present work Fe 73− x Nb x Al 4 Si 3 B 20 ( x = 5, 10) alloys have been processed by melt-spinning with the aim of studying the crystallization sequence through annealing in suitable temperatures. Melt-spun ribbons were characterized by differential scanning calorimetry (DSC), X-ray diffractometry (XRD) through Cu-Kα ( λ = 1.54 A) and synchrotron radiation ( λ = 1.77 A) and transmission electron microscopy (TEM). Soft magnetic properties were measured through the hysteresis loop tracer. In-situ XRD through synchrotron radiation was very accurate in phase identification. Fe 73− x Nb x Al 4 Si 3 B 20 ( x = 5, 10) alloys showed the possibility of forming ferromagnetic amorphous alloys composed of commercial Fe-based master alloys with fine nanocrystalline structure and good soft magnetic properties.

In the Ni–Si system, the eutectic structure composed of Ni–Ni3Si presents inherent thermal stability, allowing composite materials to be obtained with well-aligned and finely dispersed microstructures. The work reported here consisted of an investigation into the microstructure and morphology of such a eutectic alloy from the standpoint of its growth conditions. A Ni–Si eutectic alloy was processed by applying the directional solidification method at low growth rates and the rapid solidification technique using a melt-spinning process. The results indicate that samples processed under conditions close to equilibrium show a regular and aligned microstructure, while rapid solidification leads to an anomalous microstructure and the formation of a metastable phase.

In the present work the fluxing technique was applied to the Sn–51 wt.% Se hypoeutectic alloy. The aim was to study the influence of the undercooling on the microstructure of this alloy, particularly concerning the formation of oriented microstructure and even some metastability occurrence. High undercooling (63 °C) was achieved for the primary SnSe phase leading to an oriented microstructure in the firstly solidified region. Although the undercooling for the eutectic was not so high (19 °C) morphological changes were observed. The rapid movement of the interface interfered with cooperative eutectic growth producing an irregular eutectic in the first region to solidify followed by a fine lamellar and directional eutectic. In order to detect some supersaturated solid solution in the SnSe phase a precise lattice parameter measurement was done from the accurate performed X-ray diffraction (XRD) on the firstly solidified region of the sample.

Understanding the crystallization of metallic glasses is essential for the consolidation of amorphous ribbons and powders into larger bodies. In this paper, we describe the evolution of crystalline phases formed during thermal induced crystallization of amorphous Al 84 Ni 8 Co 4 Y 3 Zr melt-spun ribbons. Partially and fully crystallized samples were prepared either by heating in a differential scanning calorimeter to temperatures corresponding to each crystallization stage or by isothermal annealing in a heated oil bath at 473 and 628 K (±1 K). Isothermal annealing time ranged from 1 to 120 min. Thermal analysis. X-ray diffraction and transmission electron microscopy were used to determine both the reactions involved and the phases formed upon crystallization. Crystallization occurred in multiple stages, with nanometer-sized crystals of fcc-Al and Al 9 Co 2 phases formed in the first and second initial stages, respectively, and formation of Al 16 Ni 3 Y-like. Al 3 Y and Al 3 Zr phases upon the final reactions. Both fcc-Al and Al 9 Co 2 were found to primarily crystallize from the amorphous material. An Al 16 Ni 3 Y-like phase was formed by polymorphous crystallization of the amorphous phase remaining after the second stage.

In the present work the Zr 55 Al 10 Ni 5 Cu 30 alloy has been processed by melt spinning and die-casting into a chilled copper mold. The ribbon was fully amorphous (X-ray diffraction and transmission electron microscopy) and cast samples partially crystalline. The amorphous ribbon was crystallized and analyzed by differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. The smaller supercooled liquid range of the glassy ribbons (60 K) and partial crystallization of a larger cast sample during quenching indicate the presence of oxygen in both samples (∼0.8 at.%). Although the crystallization process of the glassy ribbon, a glass transition followed by a single crystallization peak, showed the same crystallization process as reported by the literature, the heat release and the phases formed differed. The main phases formed were Zr 2 Cu, a complex `big-cube' fcc Zr 4 Cu 2 O-type phase and a tetragonal phase, not reported before to our knowledge, containing a lattice parameter of 2.8 nm.

Mg-based nanocrystalline alloys or nanocomposites are promising materials for hydrogen storage in the solid state, which is a more effective and safer storage medium than pressurized or liquefied hydrogen. Among the many Mg-based hydrides of interest for hydrogen storage, Mg2FeH6 is in a special position due to its relatively high gravimetric capacity of 5.5% and excellent volumetric density of 150 kg H2/m3. This work involved a study of the synthesis and processing of Mg-based alloys of this type, produced by high-energy ball milling and hot extrusion. A mixture of 2Mg-Fe was prepared by high-energy ball milling under argon gas. The resulting powder was cold-pressed to produce cylindrical pre-forms, which were then extruded and the sorption properties were analyzed in a microbalance and in a Sieverts apparatus. Phase formation, microstructural evolution, desorption temperatures, and hydrogen storage capacity were analyzed by X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry, and thermogravimetric techniques. The results showed that Mg2FeH 6 was formed and the hydrogen reaction was reversible. SEM observations indicate a microstructure composed of nanosized grains in the range of 30-80 nm inside particles of about 50 μm, and Mg2FeH 6 formed mainly at the particle interfaces. The desorption temperature started at about 225 °C, reaching a maximum at 440 °C with low capacity of absorption, indicating low absorption/desorption kinetics, probably due to bulk diffusion limitations. © 2010 Elsevier B.V.

Amorphous Fe‐M‐B (M‚Zr, Nb) based alloys with nanometer-sized crystallites have attracted attention due to their magnetic properties. Although corrosion resistance is a desirable property in such alloys, no study concerning this aspect has been reported. The eAect of metalloid content and partial crystallization on corrosion resistance of Fe‐M‐B (M‚Zr, Nb) amorphous alloys, Fe84Nb7B9 ,F e 84Zr7B9 and Fe83Zr3:5Nb3:5B9Cu1, was investigated. Corrosion resistance measurements were carried out by mass loss, potentiodynamic polarization, and thermogravimetric mass gain measurements. The partial crystallization of the amorphous alloy results in a decrease of the corrosion resistance for all the compositions analyzed. We also observed a greater corrosion resistance when Nb was present in comparison to the case when Zr was present. These results are an eAect of the superficial passive film protector formed. ” 2000 Published by Elsevier Science B.V. All rights reserved.

Nano-quasicrystalline Al-Fe-Cr based alloys produced by rapid solidification processes exhibit high strength at elevated temperatures. Nevertheless, the quasicrystalline particles in these systems become unstable at high temperature limiting the industrial applications. In early works, it was observed that the use of Nb or Ta increases the stability of the Al-Fe-Cr quasicrystalline phase delaying the microstructural transformation to higher temperatures. Thus, these nano-quasicrystalline Al-based alloys have become promising new high strength material to be used at elevated temperatures in the automotive and aeronautical industries. In previous works, nano-quasicrystalline Al-Fe-Cr-Nb based alloys were obtained by rapid solidification using the melt-spinning technique. In order to obtain bulk alloys for industrial applications other fabrication routes such as powder production by gas atomization followed by compaction and extrusion are required. In the present work, the production of Al-Fe-Cr-Nb based alloys by powder atomization at laboratory scale was investigated. The powders obtained were sieved in different ranges of sizes and the microstructures were characterised by means of X-ray diffraction, scanning and transmission electron microscopy, and energy dispersive of X-ray analysis. Mechanical properties have been measured by compression tests at room temperature and at 250C. It was observed that a very high temperature is required to produce these alloys by gas atomization; the icosahedral quasicrystalline phase can be retained after the atomization in powder sizes typically under 75um, and also after the extrusion at 375C. The extruded bars were able to retain a very high strength at elevated temperature, around 60% of the yield stress at room temperature, in contrast with the 10-30% typically obtained for many commercial Al alloys. Fil: Audebert, Fernando Enrique. Universidad de Buenos Aires. Facultad de Ingeniería. Departamento de Ingeniería Mecánica. Grupo de Materiales Avanzados; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnologías y Ciencias de la Ingeniería "Hilario Fernández Long". Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías y Ciencias de la Ingeniería "Hilario Fernández Long"; Argentina Fil: Galano, Marina Lorena. University Of Oxford; Reino Unido Fil: Triveño Rios, C.. Universidade Federal Do Sao Carlos; Brasil Fil: Kasama, H.. Universidade Federal Do Sao Carlos; Brasil Fil: Peres, M.. Universidade Federal Do Sao Carlos; Brasil Fil: Kiminami, C.. Universidade Federal Do Sao Carlos; Brasil Fil: Botta, W. J.. Universidade Federal Do Sao Carlos; Brasil Fil: Bolfarini, C.. Universidade Federal Do Sao Carlos; Brasil

Ni-based bulk metallic glasses (BMGs) usually exhibit high thermal stability, excellent mechanical properties, and superior corrosion resistance. Glass forming ability (GFA), which determines the critical amorphous size, limits the application of Ni-based BMGs. In the present work, we studied the ternary Ni–Nb–Zr alloy system, which shows relatively high GFA and the presence of passive-film-forming elements Nb and Zr that are beneficial for corrosion resistance. The GFA of the Ni–Nb–Zr alloy system was evaluated by the topological instability, λ criterion, used to calculate the minimum topological instability maps which indicate the compositions where the topological instability reaches the maximum among the surrounding stable phases. Such criterion was also combined with the electronegativity difference among the elements (Δ e ) in each particular composition, which it is assumed to be related to the formation enthalpy (Δ H ) and glass stability of the corresponding alloy. The data from the literature for the maximum amorphous diameter were compared with the predictions of the topological λ criterion and with the combined criterion ( λ × Δ e ). Five compositions of rapidly solidified alloy ribbons were produced: Ni 45.5 Nb 23 Zr 31.5 , Ni 50 Nb 28 Zr 22 , Ni 57 Nb 17.5 Zr 25.5 , Ni 62 Nb 33 Zr 5, and Ni 79 Nb 8.5 Zr 12.5 . Structures of the samples were examined by X-ray diffraction (XRD). Glass transition, crystallization and melting behavior were investigated by a differential scanning calorimeter (DSC). The combined criterion ( λ × Δ e ) provided specific guidelines for locating high glass-forming alloys in the Ni–Nb–Zr alloy system.