Deformation and crystallization of Zr-based amorphous alloys in homogeneous flow regime

The purpose of this study is to experimentally investigate the interaction of inelastic deformation and microstructural changes of two Zr-based bulk metallic glasses (BMGs): Zr41.25Ti13.75Cu12.5Ni10Be22.5 (commercially designated as Vitreloy 1 or Vit1) and Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy 4, Vit4). High-temperature uniaxial compression tests were performed on the two Zr alloys at various strain rates, followed by structural characterization using differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Two distinct modes of mechanically induced atomic disordering in the two alloys were observed, with Vit1 featuring clear phase separation and crystallization after deformation as observed with TEM, while Vit4 showing only structural relaxation with no crystallization. The influence of the structural changes on the mechanical behaviors of the two materials was further investigated by jump-in-strain-rate tests, and flow softening was observed in Vit4. A free volume theory was applied to explain the deformation behaviors, and the activation volumes were calculated for both alloys.

Electron microscopy and diffraction of icosahedral twins in an aluminium—manganese alloy

The existence of icosahedral twins has been established in Al-10at.% Mn alloy. By a stereographic approach a close resemblance to the decagonal phase is pointed out. The simulation of twin diffraction patterns has been done based on the projection formalism. The physical significance of twinning in terms of hyperdimensional projection is discussed.

Characterization of Alloy-Spinel-Corundum Equilibrium in the System Fe-Ni-Al-O

The three phase equilibrium between alloy, spinel solid solution and α-alumina in the Fe-Ni-Al-O system has been fully characterized at 1823K as a function of alloy composition using both experimental and computational methods. The oxygen potential was measured using a solid state cell incorporating yttria-doped thoria as the electrolyte and Cr+ Cr2O3 as the reference electrode. Oxygen concentration of the alloy was determined by an inert gas fusion technique. The composition of the spinel solid solution, formed at the interface between the alloy and an alumina crucible, was determined by EPMA. The variation of the oxygen concentration and potential and composition of the spinel solid solution with mole fraction of nickel in the alloy have been computed using activities in binary Fe-Ni system, free energies of formation of end member spinels FeO•(1+x)Al2O3 and NiO•(1+x)Al2O3 and free energies of solution of oxygen in liquid iron and nickel, available in the literature. Activities in the spinel solid solution were computed using a cation distribution model. The variation of the activity coefficient of oxygen with alloy composition in Fe-Ni-O system was calculated using both the quasichemical model of Jacob and Alcock and the Wagner's model, with the correlation of Chiang and Chang. The computed results for the oxygen potential and the composition of the spinel solid solution are in good agreement with the measurements. The measured oxygen concentration lies between the values computed using models of Wagner and Jacob and Alcock. The results of the study indicate that the deoxidation hyper-surface in multicomponent systems can be computed with useful accuracy using data for end member systems and thermodynamic models.

Continuous ordering below the tricritical point: A critical test for the kinetic pathway in Fe-12at.% Si alloy

A critical test has been presented to establish the nature of the kinetic pathways for the decomposition of Fe-12 at.% Si alloy below the metastable tricritical point. The results, based on the measurements of saturation magnetization, establish that a congruent ordering from B2 --> D0(3) precedes the development of a B2 + D0(3) two-phase field, consistent with the predictions in 1976 of Allen and Cahn.

Effect Of Electroslag Refining On Microstructure And Mechanical-Properties Of Is-7670 Alloy

The electroslag refining technique is one of the modern tools which is capable of imparting superior mechanical and chemical properties to metals and alloys. Refining usually results in the elimination of a number of casting or solidification defects, such as shrinkage porosity, gas porosity, pipe, micro- and macro segregation. Remelting also imparts a directional grain structure apart from refining the size of the inclusions, grains and precipitates. This technique has over the years been used widely and successfully to improve the mechanical and chemical properties of steels and alloy steels which are used in the nuclear, missile, aerospace and marine industries for certain critical applications. But the application of ESR to aluminium and its alloys is only recent. This paper investigates the response of an aluminium alloy (corresponding to the Indian Specification IS: 7670) to ESR. Based on theoretical considerations and microstructural evidence it elucidates how ESR of aluminium alloys differs from that of ferrous alloys. The improvement achieved in mechanical properties of the alloy is correlated with the microstructure.

Casting and heat treatment variables of Al–7Si–Mg alloy

A review of the research work that has been carried out thus far relating the casting and heat treatment variables to the structure and mechanical properties of Al–7Si–Mg (wt-%) is presented here. Although specifications recommend a wide range of magnesium contents and a fairly high content of iron, a narrow range of magnesium contents, closer to either the upper or lower specified limits depending on the properties desired, and a low iron content will have to be maintained to obtain optimum and consistent mechanical properties. A few studies have revealed that the modification of eutectic silicon slightly increases ductility and fracture toughness and also that the effect of modification is predominant at low iron content. Generally, higher solidification rates give superior mechanical properties. Delayed aging (the time elapsed between quenching and artificial aging during precipitation hardening) severely affects the strength of the alloy. The mechanism of delayed aging can be explained on the basis of Pashley's kinetic model. It has been reported that certain trace additions (cadmium, indium, tin, etc.) neutralise the detrimental effect of delayed aging. In particular, it should be noted that delayed aging is not mentioned in any of the specifications. With reference to the mechanism by which trace additions neutralise the detrimental effect of delayed aging, various hypotheses have been postulated, of which impurity–vacancy interaction appears to be the most widely accepted.

Self accomodation morphology of martensite variants in Zr---2.5wt%Nb alloy

The role of self accomodation of the different mertensite variants controlling the morphologies of the Zr---2.5wt%Nb alloy martensite has been examined. Three distinct types of grouping of martensite variants have been found to be predominantly present. Crystallographic descriptions of these groups have been provided and the degrees of self accomodation for these have been estimated and compared with those corresponding to other possible variant groupings around the symmetry axes of the parent phase. The frequently observed 3-variant group, which shows an “indentation mark” morphology when viewed along left angle bracket111right-pointing angle bracketβ directions in the transmission electron microscope, has been seen to have the highest degree of self accomodation amongst the cases considered. Based on the observations made, a growth sequence leading to the formation of the final martensitic structure has been proposed.

Characteristics of superplasticity domain in the processing map for hot working of an Al alloy 2014---20vol.%Al2O3 metal matrix composite

The processing map for hot working of Al alloy 2014-20vol.%Al2O3 particulate-reinforced cast-plus-extruded composite material has been generated covering the temperature range 300-500 degrees C and the strain rate range 0.001-10 s(-1) based on the dynamic materials model. The efficiency eta of power dissipation given by 2m/(m + 1), where m is the strain rate sensitivity, is plotted as a function of temperature and strain rate to obtain a processing map. A domain of superplasticity has been identified, with a peak efficiency of 62% occurring at 500 degrees C and 0.001 s(-1). The characteristics of this domain have been studied with the help of microstructural evaluation and hot-ductility measurements. Microstructural instability is predicted at higher strain rates above (ls(-1)) and lower temperatures (less than 350 degrees C).

Processing map for hot working of Ni–16Cr–8Fe alloy (IN 600)

The hot deformation characteristics of IN 600 nickel alloy are studied using hot compression testing in the temperature range 850-1200-degrees-C and strain rate range 0.001-100 s-1. A processing map for hot working is developed on the basis of the data obtained, using the principles of dynamic materials modelling. The map exhibits a single domain with a peak efficiency of power dissipation of 48% occurring at 1200-degrees-C and 0.2 s-1, at which the material undergoes dynamic recrystallisation (DRX). These are the optimum conditions for hot working of IN 600. At strain rates higher than 1 s-1, the material exhibits flow localisation and its microstructure consists of localised bands of fine recrystallised grains. The presence of iron in the Ni-Cr alloy narrows the DRX domain owing to a higher temperature required for carbide dissolution, which is essential for the occurrence of DRX. The efficiency of DRX in Ni-Cr is, however, enhanced by iron addition.

Structure-Activity Relationship of Photocytotoxic Iron(III) Complexes of Modified Dipyridophenazine Ligands

Iron(III) complexes FeL(B)] (1-5) of a tetradentate trianionic phenolate-based ligand (L) and modified dipyridophenazine bases (B), namely, dipyrido-6,7,8,9-tetrahydrophenazine (dpqC in 1), dipyrido3,2-a:2',3'-c]phenazine-2-carboxylic acid (dppzc in 2), dipyrido3,2-a:2',3'-c]phenazine-11-sulfonic acid (dppzs in 3), 7-aminodipyrido3,2-a:2',3'-c]phenazine (dppza in 4) and benzoi]dipyridro3,2-a:2',3'-c]phenazine (dppn in 5), have been synthesized, and their photocytotoxic properties studied along with their dipyridophenazine analogue (6). The complexes have a five. electron paramagnetic iron(III) center, and the Fe(III)/Fe(II) redox couple appears at about 0.69 V versus SCE in DMF-0.1 M TBAP. The physicochemical data also suggest that the complexes possess similar structural features as that of its parent complex FeL(dppz)] with FeO3N3 coordination in a distorted octahedral geometry. The DNA-complex and protein-complex interaction studies have revealed that the complexes interact favorably with the biomolecules, the degree of which depends on the nature of the substituents present on the dipyridophenazine ring. Photocleavage Of pUC19 DNA by the complexes has been studied using visible light of 476, 530, and 647 nm wavelengths. Mechanistic investigations with inhibitors show formation of HO center dot radicals via a photoredox pathway. Photocytotoxicity study of the complexes in HeLa cells has shown that the dppn complex (5) is highly active in causing cell death in visible light with sub micromolar IC50 value. The effect of substitutions and the planarity of the phenazine moiety on the cellular uptake are quantified by determining the total Cellular iron content using the inductively coupled plasma-optical emission spectrometry (ICP-OES) technique. The cellular uptake increases marginally with an increase in the hydrophobicity of the dipyridophenazine ligands whereas complex 3 with dppzs shows very high uptake. Insights into the cell death mechanism by the dppn complex 5, obtained through DAFT nuclear staining in HeLa cells, reveal a rapid programmed cell death mechanism following photoactivation of complex 5 with visible light. The effect of substituent on the DNA photocleavage activity of the complexes has been rationalized from the theoretical studies.

Microstructural stability and nanoindentation of an electrodeposited nanocrystalline Ni-1.5wt.%P alloy

Microstructural stability of nanocrystalline Ni-1.5wt.%P alloy with an initial grain size of 3 nm processed by pulsed electrodeposition was studied using differential scanning calorimetry (DSC) and annealing. Microstructural characterization suggests that the observed exothermic peak during heating in DSC is related to both concurrent grain growth and Ni3P formation. Nanoindentation on samples with grain sizes from 3 to 50 nm revealed a breakdown in Hall-Petch strengthening in nano Ni-P alloy at grain sizes <= 10 nm, consistent with some previous observations. It is concluded that there is a grain boundary weakening regime for grain sizes < 10 nm, based on analysis which show that the data cannot be rationalized in terms of microstrain relaxation, variation in elastic modulus, texture evolution and duplex structure formation.

Effect of laser processing parameters on the structure of ductile iron

Laser processing of structure sensitive hypereutectic ductile iron, a cast alloy employed for dynamically loaded automative components, was experimentally investigated over a wide range of process parameters: from power (0.5-2.5 kW) and scan rate (7.5-25 mm s(-1)) leading to solid state transformation, all the way through to melting followed by rapid quenching. Superfine dendritic (at 10(5) degrees C s(-1)) or feathery (at 10(4) degrees C s(-1)) ledeburite of 0.2-0.25 mu m lamellar space, gamma-austenite and carbide in the laser melted and martensite in the transformed zone or heat-affected zone were observed, depending on the process parameters. Depth of geometric profiles of laser transformed or melt zone structures, parameters such as dendrile arm spacing, volume fraction of carbide and surface hardness bear a direct relationship with the energy intensity P/UDb2, (10-100 J mm(-3)). There is a minimum energy intensity threshold for solid state transformation hardening (0.2 J mm(-3)) and similarly for the initiation of superficial melting (9 J mm(-3)) and full melting (15 J mm(-3)) in the case of ductile iron. Simulation, modeling and thermal analysis of laser processing as a three-dimensional quasi-steady moving heat source problem by a finite difference method, considering temperature dependent energy absorptivity of the material to laser radiation, thermal and physical properties (kappa, rho, c(p)) and freezing under non-equilibrium conditions employing Scheil's equation to compute the proportion of the solid enabled determination of the thermal history of the laser treated zone. This includes assessment of the peak temperature attained at the surface, temperature gradients, the freezing time and rates as well as the geometric profile of the melted, transformed or heat-affected zone. Computed geometric profiles or depth are in close agreement with the experimental data, validating the numerical scheme.

Dry sliding wear of Al alloy 2024-Al203 particle metal matrix composites

In the present investigation, Al 2024-15vol.%Al2O3 particulate (average size, 18 mu m) composites were fabricated using the liquid metallurgy route. The wear and friction characteristics of Al alloy 2024 and Al 2024-15vol.%Al2O3p, composite in the as-extruded and peak-aged conditions were studied using a pin-on-disc machine (with a steel disc as the counterface material). The worn surfaces, subsurfaces and the debris were analysed in a scanning electron microscope.The performance of the composite in the as-extruded condition is slightly inferior to that of the unreinforced alloy. However, in the T6 condition, although the wear rates of two materials are initially comparable, the unreinforced alloy seizes while the composite does not within the tested range employed. In the as-extruded condition, the presence of Al2O3 particles is not particularly beneficial as they fracture and result in extensive localized cracking and removal of material from the surface. In the peak-aged condition, however, while the unreinforced alloy exhibits severe plastic deformation and undergoes seizure, there is no significant change in the mechanism in the case of the composite. Except in the case of the peak-aged unreinforced alloy, worn surfaces of all other materials show the presence of an iron-rich layer.

Liquid alloy semiconductors revisited - Discussion

In 1990 Enderby and Barnes reviewed the electrical properties of liquid alloys which show features associated with semiconducting behaviour. They proposed an empirical classification scheme based on the notion that some liquid semiconductors are characterized by a finite gap in σ (E), the energy-dependent conductivity (narrow definition), whereas in others σ (E) is continuous (broad definition). Interesting behaviour occurs for systems at the narrow/broad boundary and further analysis of these liquid alloys will form the subject matter of this paper. Particular attention will be focused on liquid silver chalcogenides as these offer a severe test of current theories.

Nanoporous alloy aggregates: synthesis and electrocatalytic activity

Nanoporous structures are widely used for many applications and hence there have been several efforts directed towards their synthesis. While several template-based and template-less approaches are available for monometallic systems, there is no general method for the synthesis of nanoporous multicomponent systems/alloys. We present a general template-less strategy for the synthesis of nanoporous alloy aggregates by controlled aggregation of nanoparticles in the solution phase with excellent control over morphology and composition as illustrated using AuPt, AuPd, PdPt and PtRu systems as examples. The Pt-based nanoporous clusters exhibit excellent activity for methanol oxidation with good long-term stability and CO tolerance. We show that the method can be extended to produce ternary catalysts and hence we expect our method to be widely used for the synthesis of multifunctional nanoporous structures for catalysis, sensor and drug-delivery applications.