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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.

Typically, aluminum alloys are contaminated by iron during recycling cycles. Such a procedure leads to the formation of intermetallic phases with detrimental morphology, which acts as stress risers, impairing mechanical properties and consequently hindering further mechanical processing and restricting recycling. This paper aimed at studying the solidification of an AA6061 alloy highly contaminated with iron (1.4 wt%). Spray forming processing allowed altering the solidification path of the Fe-modified AA 6061 alloy, resulting in the formation of primary α-Al15(Fe, Mn)3Si2 phase with polyhedral morphology, which traps Fe and Si at elevated temperature. Furthermore, spray forming prevented the formation of intermetallic AlFeSi phases with platelet-like morphology, such as β-AlFeSi as well as the typical Chinese script morphology, resulting in a final ductile microstructure, allowing further processing by hot extrusion.

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.

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.

In this paper, two Mg-Zn-Ca amorphous alloys were processed and their mechanical and corrosion properties were evaluated and compared. The first alloy was a new composition, Zn-rich, Mg60Zn34Ca6, designed thanks to a multifold approach involving two different criteria, topological instability, and electronic criteria. The second alloy, with less Zn content, was a well-known Mg73Zn23Ca4, used for the sake of comparison. Three kinds of rapidly solidified samples were processed for each composition: ribbons, wedge, and cylindrical samples. The new composition showed much better glass-forming ability and superior corrosion and mechanical properties than the Zn-poorer composition. The effect of Fe content, a typical contaminant in Mg-based alloys, was also evaluated. Electrochemical results in amorphous and in crystalline samples showed that increasing iron to certain amounts has no influence on the corrosion resistance of the investigated alloys. Keywords: Mg-Zn-Ca amorphous alloys, Design of amorphous alloys, Contaminant effect, Mechanical and corrosion properties, Biomaterial

A series of Al-rich Al-Mn-Ce alloys have been chill cast in copper molds and some were subjected to subsequent heat treatments. For all compositions studied, the ternary Al20Mn2Ce phase is formed as the primary phase surrounded by different constituents. The mechanical properties as a function of composition and heat treatment are presented and illustrate that this system is very versatile and that it is possible to tailor the compositions to produce alloys with high yield strengths, alloys with high hardnesses (for wear applications), and alloys with reasonably high ductilities. Alloys with high yield strengths and some ductility are obtained when the microstructure contains the ternary phase surrounded by the Al-Al11Ce3 eutectic constituent. Alloys with high hardnesses, can be obtained at higher Mn levels where the ternary phase and other intermetallics constitute most of the structure. Alloys with relatively high ductilities are possible at lower Ce and Mn levels where a metastable FCC solid solution of Mn in Al forms surrounding the ternary phase. Although the finely-distributed ternary phase is metastable, it appears to be relatively resistant to coarsening or decomposition. Finally, it is shown that Ce can be substituted by Mischmetal with no significant changes in either microstructure or properties. Keywords: Aluminum alloys, Al-Mn-Ce, Chill mold casting, High specific strength, Dispersion hardening, Electron microscopy

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 (

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.

In this paper the chemical composition of the supermartensitic stainless (SM) was modified with the addition of small boron contents (0.3, 0.5 and 0.7 wt.%) and processed by spray forming aiming the development of functionalized stainless steel with higher wear resistance. The addition of boron to the SM leads to the formation of continuous network of M2B type borides uniformly distributed in the refined microstructure promoted by the spray forming process. The wear resistance was evaluated by two different methodologies: (1) the standardized dry sand/rubber wheel test (ASTM G65); and (2) a plate-on-cylinder (POC) wear test which was designed to simulate in laboratorial scale the tribosystems found in wear of risers and casings. It was shown that the wear mechanisms that take place in both tests are quite different, but in all cases increasing the boron content is always accompanied by an increase in the wear resistance. Electrochemical analyses were performed to evaluate the corrosion resistance of the designed alloys. It could be seen that corrosion properties similar to the commercial SM can be achieved in the SM modified with 0.7 wt.% of boron if an over content of chromium is added to the chemical composition. Keywords: Spray forming, Supermartensitic stainless steel, Borides, Wear resistance, Corrosion resistance

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.

Spray forming (SF) can be classified as a two-stage manufacturing process in which solidification begins during particle flight, a relatively rapid solidification step that ends as the deposit builds up, with the remaining liquid droplets solidifying at considerably slower rates. Due to the high cooling rate of the atomization step and the special conditions of deposit buildup, with incoming materials dynamically refining the solidifying material, as-sprayed deposits typically display a fine-scale microstructure which may also exhibit some extended solid solubility and metastable phases. Our group has studied several alloys in order to investigate the potential formation of novel microstructures by this process. This paper describes some of the results obtained by spray forming of aluminum- and iron-based alloys, whose compositions derive from rapid solidification studies aimed at obtaining amorphous structures. Al85Y8Ni5Co2, Fe83Zr3.5Nb3.5B9Cu1, [(Fe0.6Co0.4)0.75B0.2Si0.05]96Nb4, and Fe63Nb10Al4Si3B20 glass-forming alloys were processed. Formation of amorphous phase was observed throughout the deposit of the Al-based alloy processed at a high G/M ratio, which was not observed in the Fe-based alloys. In addition, the [(Fe0.6Co0.4)0.75B0.2Si0.05]96Nb4 alloy, which displayed the highest glass-forming ability among the Fe-based alloys, showed a high volume percent of amorphous phase formation up to 4mm thickness of the deposit, a similar value obtained for this alloy when processed by copper mold casting.

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.

A bulk sample of Al–Fe–Cr–Ti alloy with adequate composition to form quasicrystalline phases has been surface remelted, using laser processing techniques, to produce a quasicrystalline surface coating. After the laser treatment, the samples were characterized by X-ray diffractometry, differential scanning calorimetry, scanning electron microscopy and scanning/transmission electron microscopy. The results indicate the feasibility of producing low-density coatings containing quasicrystalline phases by laser remelting on a bulk sample of an aluminum-based alloy.

A combination of an extension of the topological instability “λ criterion” and a thermodynamic criterion were applied to the Al–La system, indicating the best range of compositions for glass formation. Alloy compositions in this range were prepared by melt-spinning and casting in an arc-melting furnace with a wedge-section copper mold. The GFA of these samples was evaluated by X-ray diffraction, differential scanning calorimetry and scanning electron microscopy. The results indicated that the γ* parameter of compositions with high GFA is higher, corresponding to a range in which the λ parameter is greater than 0.1, which are compositions far from Al solid solution. A new alloy was identified with the best GFA reported so far for this system, showing a maximum thickness of 286 μm in a wedge-section copper mold.

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.

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.

Despite, the homogeneous and refined microstructure, spray-formed deposits of binary Fe–Si alloys with high silicon content are still difficult to hot/cold roll due to A2-disordered/B2-ordered reactions. The addition of aluminum to Fe–Si alloys may be able to keep the A2-disordered phase metastable at temperatures below 973 K, allowing the deposits to be rolled without cracking while adequately maintaining their magnetic properties. This study is a first attempt to investigate the microstructure and the magnetic properties of spray-formed Fe–3 wt.%Si–3.5 wt.%Al alloy. Argon and nitrogen were used as atomization gases. The addition of aluminum to Fe–Si alloys led to the successful production of thin sheets (0.5 mm thickness) from spray-formed deposits when using argon as atomizing gas. In contrast, the use of nitrogen led to the formation of AlN particles, resulting in excessive brittleness of the spray-formed deposit, which fractured during cooling to room temperature. Otherwise, the magnetic properties of the Fe–3.0 wt.%Si–3.5 wt.%Al alloy performed very well when compared with binary Fe–6.5 wt.%Si, especially when spray formed with argon.

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 this study the Fe63Nb10Al4Si3B20 (at.%) alloy was processed by spray forming with the aim of investigate the formation of amorphous phases and novel microstructures by the high cooling rate involved in this process. The gas/metal mass flow rate used was 0.25, and nitrogen was used as the atomization gas. The resulting deposit of a mass of about 1.2 kg, as well as the overspray powder, with a median particle diameter about 120 μm, were characterized by using X-ray diffractometry, differential scanning calorimetry and scanning and transmission electron microscopy with energy of dispersive spectroscopy. Magnetic properties were measured through hysteresis loop tracer equipment. The overspray powder presented a mass median diameter of d50 ≅ 120 μm and an increasing of amorphous phase volume fraction with decreasing of particle size. The microstructure of the deposit was heterogeneous varying with the thickness, presenting at center region 20 mm and at border 1 mm with different porosities 5 and 10%, respectively. The thicker region presented fully crystalline microstructure whereas the thinner presented about 75% amorphous phase. The phases identified in both deposit and overspray powder were: amorphous, α-Fe, Fe23B6, FeB and FeNbB. Amorphous phase formation in the thinner region of the deposit and the absence in the thicker region indicates that the resulting amorphous phase depend on the maintenance of amorphous phase formed during atomization that might be controlled by process parameters. Spray forming of Fe-based amorphous alloys followed by hot consolidation in T

The microstructure and the tensile properties of an Al–8.9 wt.% Si–3.2 wt.% Cu–0.9 wt.% Fe–0.8% Zn alloy processed by spray forming was investigated. The porosity level, the conditions of the heat treatment applied and the presence/addition of certain alloying elements to this alloy is known to greatly affect its mechanical properties. In this work, the alloy was gas atomized with argon and deposited onto a copper substrate, extruded at 623 K and heat treated to the T6 temperature Mg was added to some heats. Room temperature tensile tests of the spray formed and extruded alloy showed significant increase of elongation when compared with the values observed for the as-spray formed deposits. This result can be ascribed to the decrease of porosity promoted by the extrusion process. The spray formed and extruded, T6 heat-treated samples showed significant increase of strength without lowering the elongation results. The addition of 0.3 wt.% Mg increased the response to the heat treatment process.

Aluminum additions to brittle Fe–6.5 wt.% Si alloys made possible the mechanical processing of these alloys at lower temperatures and thus being determinant in the development of the texture. The aim of this work was to analyse the evolution of the crystallographic texture of a spray-formed (SF) Fe–6.5 wt.% Si–1.0 wt.% Al during rolling operation for thin sheets production. The SF deposit was warm-rolled and then air cooled to obtain partial recrystallisation. The initial texture (0 1 1) [ 0 1 ¯ 1 ] [1 0 0] (// to normal direction-ND) of the deposit was changed to approximately (0 1 3) [ 1 1 ¯ 0 ] [1 1 0] (8° from ND) after the last reduction step. The maxima intensities of texture was found at 700 °C (89% of reduction) showing the influence of rolling temperature; after warm-rolling the entire texture changes to a partial ND fibre running from {0 0 1} to {1 1 0}, with negligible Goss intensities. The transition away from an ND fibre texture in the lattermost case (99.5% reduction) was in turn associated with the near-absence of shear bands.

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.

The glass former Fe 83 Zr 3.5 Nb 3.5 B 9 Cu 1 (at.%) alloy was processed by spray forming. The aim was to investigate the possibility of forming novel microstructures using this process. The ratio between the gas mass flow rate and the metal mass flow rate used was 0.23, and nitrogen was used as atomization gas. The resulting deposit, weighting about 0.8 kg, as well as the overspray powder with a median particle diameter about 150 μm, were characterized by using X-ray diffratometry, differential scanning calorimetry and scanning electron microscopy with energy dispersive spectroscopy. Saturation induction ( B s ), maximum permeability ( μ max ) and coercive field ( H c ) were measured. The overspray powder showed a microstructure consisting of amorphous and α-Fe phases. The volume fraction of the amorphous phase decreased as the granulometric size range increased. The deposit presented fully crystalline structure with α-Fe, Fe 3 Nb, Fe 2 Zr and Fe 2 B phases. The formation of amorphous phase in the overspray and its absence in the deposit indicates that the deposit was formed by the impacting of a high volume fraction of fully liquid droplets, providing temperature and time enough for complete crystallization of the deposit.

The microstructure and the tensile properties of an Al–8.9 wt.% Si–3.2 wt.% Cu–0.9 wt.% Fe–0.8% Zn alloy processed by spray forming was investigated. The alloy was gas atomized with argon and deposited onto a copper substrate. The microstructure was evaluated by optical microscopy (OM), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Small faceted dispersoids observed surrounding equiaxial α-Al matrix were identified by SEM–EDS as silicon particles. Sand cast samples with the same composition showed a columnar dendritic α-Al matrix, Al–Si eutectic, polyhedric α-AlFeSi and needle-like β-AlFeSi intermetallics. In the spray formed material the formation of the Al–Si eutetic was suppressed, and the formation of the α-AlFeSi and β-AlFeSi intermetallics was strongly reduced. The fine and homogeneous microstructure showed an aluminium matrix with grain size ranging from 30 to 40 μm, and particle size of the silicon dispersoids having a mean size of 12 μm. Room temperature tensile tests of the spray formed alloy showed relative increasing of strength and elongation when compared with the values observed for the conventionally cast counterparts. These results can be ascribed to the refined microstructure and the scarce presence of intermetallics of the spray formed material.

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.

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.

Mechanical alloying, MA, is a high-energy ball milling technique, in which elemental blends are milled to achieve alloying at atomic level. This communication describes the results of an investigation on the phase transformation of a mixture of Fe and Si powders with 6wt%Si during MA processing. Besides the verification of the effect of milling time on the structure and on the compositional homogeneity, this study was undertaken in order to confirm, by using TEM technique, the possibility of amorphous phase formation for Si content lower than 17.7wt%.

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.