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Solute- and solvent-based electromotive force cells for activity measurements of electroactive species in molten salts

A novel combination of solute- and solvent-based electrodes was used to determine the activities of NdCl 3 and GdCl 3 in molten LiCI-KCI eutectic using electromotive force measurements across a broad concentration range of dissolved electroactive species. First, an electrochemical cell using solute-based electrodes was used to define the relative activity of each species as a function of concentration and the concentration region in which Henry's law was applicable. Next, the electromotive force between a solute-based electrode with a known NdCl 3 or GdCl 3 concentration and a solvent-based electrode with a known electromotive force was measured. The solvent-based electrode potential was converted to the Lithium Eutectic Electrode (LEE) potential, which allowed the activity of dissolved NdCl 3 and GdCl 3 to be calculated at the concentrations measured using the solute-based electrodes. The described two-cell method uses electromotive force measurements to accurately determine the activity of electroactive species over a wide concentration range and provides a simple approach to closing the knowledge gap of thermochemical properties of molten salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal growth, structural and physicochemical studies of novel binary organic complex: 4-chloroaniline-3-hydroxy-4-methoxybenzaldehyde

The solid-state reaction, which is solvent free and green synthesis, has been adopted to explore the novel compound. The phase diagram of 4-chloroaniline (CA) and 3-hydroxy-4-methoxybenzaldehyde (HMB) system shows the formation of a novel 1:1 molecular complex, and two eutectics on either sides of complex. Thermochemical studies of complex and eutectics have been carried out for various properties such as heat of fusion, entropy of fusion, Jackson's parameters, interfacial energy and excess thermodynamic functions. The formation of molecular complex was also studied by IR, NMR, elemental analysis and UV-Vis absorption spectra. The single crystal of molecular complex was grown and its XRD study confirms the formation of complex and identifies the crystal structure and atomic packing of crystal of complex. Transmission spectra of grown crystal of the complex show 70% transmittance efficiency with cut off wavelength 412 nm. The band gap and refractive index of the crystal of complex have also been studied. - Graphical abstarct: Exploiting phase diagram study and solvent free synthesis a novel compound was synthesized and its single crystal growth, atomic packing, energy band gap and refractive index were studied. Highlights: Black-Right-Pointing-Pointer Novel organic complex was synthesized using Green or solvent free synthesis. Black-Right-Pointing-Pointer Phase diagram study provided the information to identify the worthy composition of novel complex. Black-Right-Pointing-Pointer The single crystal of the sufficient size was grown from the ethanol solution. Black-Right-Pointing-Pointer Crystal analysis suggested that the covalent bond is formed between the two parent compounds. Black-Right-Pointing-Pointer The transmittance of the crystal was found to be 70% and it was transparent from 412 to 850 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxygen trapped by rare earth tetrahedral clusters in Nd{sub 4}FeOS{sub 6}: Crystal structure, electronic structure, and magnetic properties

Single crystals of Nd{sub 4}FeOS{sub 6} were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd{sub 4}MnOSe{sub 6}-type structure (P6{sub 3}mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å{sup 3}, Z=2), featuring parallel chains of face-sharing [FeS{sub 6×1/2}]{sup 4−} trigonal antiprisms and interlinked [Nd{sub 4}OS{sub 3}]{sup 4+} cubane-like clusters. Oxygen atoms were found to be trapped by Nd{sub 4} clusters in the [Nd{sub 4}OS{sub 3}]{sup 4{sub +}} chains. Structural differences among Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6} and the related La{sub 3}CuSiS{sub 7}− and Pr{sub 8}CoGa{sub 3}-type structures have been described. Magnetic susceptibility measurements on Nd{sub 4}FeOS{sub 6} suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions. - Graphical abstract: Trapping of oxygen in Nd{sub 4} tetrahedral clusters results in the formation of the Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6}, in contrast to the La{sub 3}CuSiS{sub 7}-type oxygen-free Nd{sub 4}FeS{sub 7} and related Pr{sub 8}CoGa{sub 3}-type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd{sub 4}FeOS{sub 6} were grown using self-flux method. • Oxygen was found trapped by Nd{sub 4} tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nd{sub 8}Co{sub 4−x}Al{sub x}Ge{sub 2}C{sub 3}: A case study in flux growth of lanthanide-rich intermetallics

The intermetallic Nd{sub 8}Co{sub 4−x}Al{sub x}Ge{sub 2}C{sub 3} (x≈0.65) was prepared from reaction of germanium and carbon in Nd/Co eutectic flux in an alumina crucible. This phase exhibits a new structure type in orthorhombic space group Pbcm, with unit cell parameters a=8.001(1) Å, b=11.696(2) Å, c=15.020(3) Å (Z=4; R{sub 1}=0.0234). The structure features germanium-centered neodymium clusters Ge@Nd{sub 9} which share faces to form layers separated by zigzag chains of cobalt atoms capped by carbon. Density of states calculations confirm that this compound is metallic, and indicate that the cobalt should not have a magnetic moment. This is supported by magnetic susceptibility measurements which show a low temperature ferromagnetic ordering at T{sub C}=50 K due to the Nd{sup 3+} ions. Magnetization field dependence studies on single crystals indicate this compound is a strong ferromagnet with large anisotropy; the Nd{sup 3+} magnetic moments align along the a-axis. - Graphical abstract: Nd{sub 8}Co{sub 4−x}Al{sub x}Ge{sub 2}C{sub 3} (x≈0.65) contains germanium-centered neodymium clusters Ge@Nd{sub 9} which share faces to form layers separated by zigzag chains of cobalt atoms capped by carbon. - Highlights: • Nd{sub 8}Ge{sub 2}Co{sub 3.35}Al{sub 0.65}C{sub 3} grows as large crystals from reactions in Nd/Co eutectic flux. • Structure features Ge@Nd{sub 9} clusters and zigzag cobalt chains capped by carbon. • Cobalt has no magnetic moment; Nd{sup 3+} ion moments order ferromagnetically. • Hard ferromagnet with strong anisotropy below T{sub C} of 50 K. • Flux growth and structural trends of lanthanide-rich intermetallics are reviewed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single crystal growth and characterization of Na{sub x}Ln{sub 1−x}MoO{sub 4}, Ln=La, Ce, Pr, Nd, Sm, and Eu (x=0.397–0.499)

Single crystals of La{sub 0.516(3)}Na{sub 0.484(3)}MoO{sub 4}, Ce{sub 0.512(2)}Na{sub 0.488(2)}MoO{sub 4}, Pr{sub 0.502(2)}Na{sub 0.498(2)}MoO{sub 4,} Nd{sub 0.501(2)}Na{sub 0.499(2)}MoO{sub 4}, Sm{sub 0.509(2)}Na{sub 0.491(2)}MoO{sub 4}, and Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} were grown for the first time out of an alkali metal halide eutectic flux. All compounds crystallize in the tetragonal space group I4{sub 1}/a. UV/Vis measurements show the presence of an absorption edge for all compounds except Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4}. The temperature dependence of the magnetic susceptibility was measured for all compounds and found to be paramagnetic across the entire 2–300 K temperature range measured. - Graphical abstract: Single crystals of La{sub 0.516(3)}Na{sub 0.484(3)}MoO{sub 4}, Ce{sub 0.512(2)}Na{sub 0.488(2)}MoO{sub 4}, Pr{sub 0.502(2)}Na{sub 0.498(2)}MoO{sub 4,} Nd{sub 0.501(2)}Na{sub 0.499(2)}MoO{sub 4}, Sm{sub 0.509(2)}Na{sub 0.491(2)}MoO{sub 4}, and Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} were grown for the first time out of an alkali metal halide eutectic flux. All compounds crystallize in the tetragonal space group I4{sub 1}/a. Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} was found to possess the highest Mo{sup 5+} content at 20.6%. UV/Vis, magnetic susceptibility, and a bond valence sum analysis were performed on all samples. Display Omitted - Highlights: • Six lanthanide sodium molybdates have been synthesized and characterized. • An in situ reduction was carried out using Mo as a metal reducing agent. • UV/Vis and magnetic susceptibility data were collected. • Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} was found to possess the highest Mo{sup 5+} content at 20.6%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and calculated phases in two as-cast and annealed Mg-Zn-Y alloys

The CALPHAD (Calculation of Phase Diagram) method was used to select ternary alloys from Mg-Zn-Y system, aimed at determining the role of precipitates in the microstructure and texture evolution of Mg during and after deformation. The selected alloys are Mg-6Zn-1.2Y and Mg-5Zn-2Y. The constituent phases in the as-cast Mg-6Zn-1.2Y alloy are {alpha}-Mg solid solution phase and I (Mg{sub 3}YZn{sub 6}) intermetallic phase. The as-cast Mg-5Zn-2Y alloy is composed of {alpha}-Mg, I and W (Mg{sub 3}Y{sub 2}Zn{sub 3}) phases. The intermetallics in the two alloys form by eutectic reaction, which in Mg-5Zn-2Y alloy results in initially W-phase formation and ultimately I-phase formation during solidification. After heat treatment, the Mg-6Zn-1.2Y and Mg-5Zn-2Y alloys contain nearly the same amount of ternary intermetallics (I and W phases, respectively) in equilibrium with {alpha}-Mg solid solution phase. The main solute in {alpha}-Mg phase is Zn with the same amount in the two alloys. The type and quantity of the phases obtained experimentally disagree with the results obtained from the thermodynamic database. One important discrepancy is that, in Mg-6Zn-1.2Y alloy, the I phase is not stable at the temperature of 430 Degree-Sign C, and that the W phase is the stable phase at this temperature. The differences in the experimental and calculated data indicate that the Mg-Zn-Y system requires to be reassessed with more experimental data. - Highlights: Black-Right-Pointing-Pointer Mg-6Zn-1.2Y and Mg-5Zn-2Y alloys were selected by FactSage Trade-Mark-Sign Thermodynamic software. Black-Right-Pointing-Pointer The I and W intermetallics in the two alloys form by eutectic reaction. Black-Right-Pointing-Pointer The alloys contain similar amounts of different intermetallics in equilibrium with {alpha}-Mg. Black-Right-Pointing-Pointer In Mg-6Zn-1.2Y, the I phase is not stable at the temperature of 430 Degree-Sign C. Black-Right-Pointing-Pointer The hardness of W phase is determined to be lower than that of I phase.

36 MATERIALS SCIENCE↗

Effects of high magnetic field on the evolutions of constituent phases in 7085 aluminum alloy during homogenization

The evolutions of coarse constituent phases in homogenized 7085 aluminum alloy at different conditions with or without the application of 12 T high magnetic field were examined by using differential scanning calorimetry, scanning electronic microscope, energy dispersive spectroscopy and X-ray diffraction. It is found that the main constituent phases including quaternary phase T(AlZnMgCu), Al{sub 7}Cu{sub 2}Fe, and AlTiCuFeSi are present in as-cast 7085 alloy. During homogenization, {alpha} + T eutectics become discontinuous and spheroidized, and Al{sub 2}CuMg phase nucleates and grows along {alpha} + T eutectics. High magnetic field significantly accelerates the melting of quaternary phase T and Al{sub 2}CuMg phase. When the alloy homogenized at 460 Degree-Sign C/10 h + 480 Degree-Sign C/8 h with 12 T magnetic field, the least amount of constituent phases is obtained. - Highlights: Black-Right-Pointing-Pointer Most of published reports of magnetic field are focused on ferrous alloys. Black-Right-Pointing-Pointer Effect of magnetic field on microstructure of 7085 during homogenization is studied. Black-Right-Pointing-Pointer Magnetic field accelerates the melting of AlZnMgCu and S phase.

36 MATERIALS SCIENCE↗

Real time synchrotron X-ray observations of solidification in hypoeutectic Al–Si alloys

This paper demonstrates how recent advances in synchrotron technology have allowed for the real-time X-ray imaging of solidification in Al–Si alloys, despite the small difference in atomic number of these elements. The experiments performed at the SPring-8 synchrotron, involved imaging the solidification of Al–1wt.%Si and Al–4wt.%Si alloys under a low-temperature gradient and a cooling rate of around 0.3 °C/s. The nucleation and growth of the primary aluminum grains as well as the onset of eutectic solidification were clearly observed. In the alloys containing Al–4wt.%Si, contrast was sufficient to characterize the nucleation rate and growth velocity of the aluminum grains. The importance of improving observation of solidification in the Al–Si system by increasing the time resolution during critical events is discussed. - Highlights: • A synchrotron technique was used to observe solidification of Al-Si alloys. • Nucleation, coarsening, and the onset of eutectic solidification were observed. • Images captured are suitable for quantitative analysis. • The resolution that was obtained should be possible for most aluminum alloys.

36 MATERIALS SCIENCE↗

Effect of re-melting on particle distribution and interface formation in SiC reinforced 2124Al matrix composite

The interface between metal matrix and ceramic reinforcement particles plays an important role in improving properties of the metal matrix composites. Hence, it is important to find out the interface structure of composite after re-melting. In the present investigation, the 2124Al matrix with 10 wt.% SiC particle reinforced composite was re-melted at 800 °C and 900 °C for 10 min followed by pouring into a permanent mould. The microstructures reveal that the SiC particles are distributed throughout the Al-matrix. The volume fraction of SiC particles varies from top to bottom of the composite plate and the difference increases with the decrease of re-melting temperature. The interfacial structure of re-melted 2124Al–10 wt.%SiC composite was investigated using scanning electron microscopy, an electron probe micro-analyzer, a scanning transmission electron detector fitted with scanning electron microscopy and an X-ray energy dispersive spectrometer. It is found that a thick layer of reaction product is formed at the interface of composite after re-melting. The experimental results show that the reaction products at the interface are associated with high concentration of Cu, Mg, Si and C. At re-melting temperature, liquid Al reacts with SiC to form Al{sub 4}C{sub 3} and Al–Si eutectic phase or elemental Si at the interface. High concentration of Si at the interface indicates that SiC is dissociated during re-melting. The X-ray energy dispersive spectrometer analyses confirm that Mg- and Cu-enrich phases are formed at the interface region. The Mg is segregated at the interface region and formed MgAl{sub 2}O{sub 4} in the presence of oxygen. The several elements identified at the interface region indicate that different types of interfaces are formed in between Al matrix and SiC particles. The Al–Si eutectic phase is formed around SiC particles during re-melting which restricts the SiC dissolution. - Highlights: • Re-melted composite shows homogeneous particle distribution • Thick reaction products are observed at the interface • Carbide is identified at interface due to SiC dissolution at high temperature • Reaction products are also Si enrich phase • Mg and Cu segregated and formed MgAl{sub 2}O{sub 4}, CuMgAl{sub 2} phase at grain boundary.

36 MATERIALS SCIENCE↗

Effects of gas to melt ratio on the microstructure of an Al–10.83Zn–3.39Mg–1.22Cu alloy produced by spray atomization and deposition

Various gas to melt ratios (GMR) that govern the cooling rate of spray forming can be achieved through controlling the atomizer form and the atomization pressure. The effect of the GMR on microstructures of an Al–10.83Zn–3.39Mg–1.22Cu alloy produced through spray forming has been studied using electron microscopy. When the GMR is high at 3.5, dendritic structure and quasi-crystalline i-Mg{sub 32}(AlZn){sub 49} particles inherited from the original powders can be observed. Spray forming at medium GMR of 2.3 produces equiaxed α-Al grains and MgZn{sub 2} phase that discontinuously distributes along the grain boundaries and within the grains as small particles. The low GMR of 1.4 corresponds to low cooling rate. Coarse and equiaxed α-Al grains together with eutectic structure consisting of b.c.c.-Mg{sub 32}(AlZn){sub 49} and α-Al phases along the grain boundaries are obtained. - Highlights: • At high GMR, the broken fragments and i-Mg{sub 32}(AlZn){sub 49} quasicrystal are observed. • At medium GMR, microstructure consists of α-Al equiaxed grains and MgZn{sub 2} phase. • At low GMR, the coarsened α-Al grains and bcc-Mg{sub 32}(AlZn){sub 49} eutectic appear.

36 MATERIALS SCIENCE↗

A comparative study of quantitative microsegregation analyses performed during the solidification of the Ni-base superalloy CMSX-10

Quantitative microsegregation analyses were systematically carried out during the solidification of the Ni-base superalloy CMSX-10 to clarify the methodological effect on the quantification of microsegregation and to fully understand the solidification microstructure. Three experimental techniques, namely, mushy zone quenching (MZQ), planar directional solidification followed by quenching (PDSQ), and random sampling (RS), were implemented for the analysis of microsegregation tendency and the magnitude of solute elements by electron probe microanalysis. The microprobe data and the calculation results of the diffusion field ahead of the solid/liquid (S/L) interface of PDSQ samples revealed that the liquid composition at the S/L interface is significantly influenced by quenching. By applying the PDSQ technique, it was also found that the partition coefficients of all solute elements do not change appreciably during the solidification of primary γ. All three techniques could reasonably predict the segregation behavior of most solute elements. Nevertheless, the RS approach has a tendency to overestimate the magnitude of segregation for most solute elements when compared to the MZQ and PDSQ techniques. Moreover, the segregation direction of Cr and Mo predicted by the RS approach was found to be opposite from the results obtained by the MZQ and PDSQ techniques. This conflicting segregation behavior of Cr and Mo was discussed intensively. It was shown that the formation of Cr-rich areas near the γ/γ′ eutectic in various Ni-base superalloys, including the CMSX-10 alloy, could be successfully explained by the results of microprobe analysis performed on a sample quenched during the planar directional solidification of γ/γ′ eutectic. - Highlights: • Methodological effect on the quantification of microsegregation was clarified. • The liquid composition at the S/L interface was influenced by quenching. • The segregation direction of Cr varied depending on the experimental techniques. • Cr and Mo segregation in Ni-base superalloys was fully understood.

36 MATERIALS SCIENCE↗

The use of a directional solidification technique to investigate the interrelationship of thermal parameters, microstructure and microhardness of Bi–Ag solder alloys

Bi–Ag alloys have been stressed as possible alternatives to replace Pb-based solder alloys. Although acceptable melting temperatures and suitable mechanical properties may characterize such alloys, as referenced in literature, there is a lack of comprehension regarding their microstructures (morphologies and sizes of the phases) considering a composition range from 1.5 to 4.0 wt.%Ag. In order to better comprehend such aspects and their correlations with solidification thermal parameters (growth rate, v and cooling rate, T-dot), directional solidification experiments were carried out under transient heat flow conditions. The effects of Ag content on both cooling rate and growth rate during solidification are examined. Microstructure parameters such as eutectic/dendritic spacing, interphase spacing and diameter of the Ag-rich phase were determined by optical microscopy and scanning electron microscopy. The competition between eutectic cells and dendrites in the range from 1.5 to 4.0 wt.%Ag is explained by the coupled zone concept. Microhardness was determined for different microstructures and alloy Ag contents with a view to permitting correlations with microstructure parameters to be established. Hardness is shown to be directly affected by both solute macrosegregation and morphologies of the phases forming the Bi–Ag alloys, with higher hardness being associated with the cellular morphology of the Bi-2.5 and 4.0 wt.%Ag alloys. - Highlights: • Asymmetric zone of coupled growth for Bi–Ag is demonstrated. • Faceted Bi-rich dendrites have been characterized for Bi–1.5 wt.%Ag alloy. • Eutectic cells were shown for the Bi-2.5 and 4.0 wt.%Ag solder alloys. • Interphase spacing relations with G × v are able to represent the experimental scatters. • Hall-Petch type equations are proposed relating microstructural spacings to hardness.

36 MATERIALS SCIENCE↗

The sequence of intermetallic formation and solidification pathway of an Al–13Mg–7Si–2Cu in-situ composite

The phase transformation sequence and solidification behaviour of an Al–13Mg–7Si–2Cu in-situ composite was examined using a combination of computer-aided cooling curve thermal analysis and interrupted quenching techniques. Five different phases were identified by analysing the derivative cooling curves, the X-ray diffraction profile, optical and scanning electron microscopy images and the corresponding energy dispersive spectroscopy. It has been found that the solidification of this alloy begins with primary Mg{sub 2}Si precipitation and continues with the formation of eutectic Al–Mg{sub 2}Si, followed by Al{sub 5}FeSi and simultaneous precipitation of Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} and Al{sub 2}Cu complex intermetallic phases. The formation of the last three intermetallic compounds changes the solidification behaviour of these composites remarkably due to their complex eutectic formation reactions. The solidification of the alloy, calculated using the Factsage thermochemical analysis software, has demonstrated a good agreement with the experiments in terms of compound prediction, their weight fractions and reaction temperatures. - Highlights: • Solidification path of a commercial Al-13Mg-7Si-2Cu composite was characterized. • Five different phases were identified and then confirmed with EDS and XRD results. • Mg{sub 2}Si, Al-Mg{sub 2}Si,Al{sub 5}FeSi (β),Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} (Q) and Al{sub 2}Cu(θ) precipitated respectively. • Solidification was predicted using the Factsage thermochemical analysis software.

36 MATERIALS SCIENCE↗

Effects of W on microstructure of as-cast 28 wt.%Cr–2.6 wt.%C–(0–10)wt.%W irons

Microstructures of as-cast 28 wt.%Cr–2.6 wt.%C irons containing (0–10)wt.%W with the Cr/C ratio about 10 were studied and related to their hardness. The experimental irons were cast into dry sand molds. Microstructural investigation was performed by light microscopy, X-ray diffractometry, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectrometry. It was found that the irons with 1 to 10 wt.%W addition was hypereutectic containing large primary M{sub 7}C{sub 3}, whereas the reference iron without W addition was hypoeutectic. The matrix in all irons was austenite, partly transformed to martensite during cooling. The volume fractions of primary M{sub 7}C{sub 3} and the total carbides increased, but that of eutectic carbides decreased with increasing the W content of the irons. W addition promoted the formation of W-rich M{sub 7}C{sub 3}, M{sub 6}C and M{sub 23}C{sub 6}. At about 4 wt.%W, two eutectic carbides including M{sub 7}C{sub 3} and M{sub 6}C were observed together with primary M{sub 7}C{sub 3}. At 10 wt.%W, multiple carbides including primary M{sub 7}C{sub 3}, fish-bone M{sub 23}C{sub 6}, and M{sub 6}C were observed. M{sub x}C where x = 3 or less has not been found due possibly to the high M/C ratio in the studied irons. W distribution to all carbides has been determined increasing from ca. 0.3 to 0.8 in mass fraction as the W content in the irons was increased. W addition led to an increase in Vickers macro-hardness of the irons up to 671 kgf/(mm){sup 2} (HV30/15) obtained from the iron with 10 wt.%W. The formation of primary M{sub 7}C{sub 3} and aggregates of M{sub 6}C and M{sub 23}C{sub 6} were the main reasons for hardness increase, indicating potentially improved wear performance of the as-cast irons with W addition. - Highlights: • W addition at 1 up to 10 wt.%W to Fe–28Cr–2.6C produced “hypereutectic” structure. • W addition promoted the formation of W-rich M{sub 7}C{sub 3}, M{sub 6}C and M{sub 23}C{sub 6}. • M{sub 23}C{sub 6} has higher Fe/Cr and W/Cr atm% ratios than those in M{sub 7}C{sub 3}. • Si content and high W content over about 11 atm% are characteristics of M{sub 6}C. • Primary M{sub 7}C{sub 3} and aggregates of M{sub 6}C and M{sub 23}C{sub 6} increased the alloy macro-hardness.

36 MATERIALS SCIENCE↗

Precipitates in a quasicrystal-strengthened Al–Mn–Be–Cu alloy

In this work, an Al–Mn–Be–Cu alloy was studied containing a primary and eutectic icosahedral quasicrystalline phase in the as-cast microstructure. Special attention was given to a transmission electron microscopy investigation of precipitates formed within the aluminium solid solution (Al{sub ss}) at different temperatures. At 200 °C, only binary Al–Cu precipitates (θ′) were formed. At 300 °C, icosahedral quasicrystalline (IQC) precipitates prevailed with a crystallographic orientation relationship with the Al{sub ss.} The rods of the T-phase (Al{sub 20}Mn{sub 3}Cu{sub 2}) which were precipitated above 400 °C, also had a specific orientation relationship with the Al{sub ss}. The primary and eutectic IQC microstructural constituent started to transform rapidly to the T-phase and Be{sub 4}Al(Mn,Cu) at 500 °C. - Highlights: • In a quasicrystal-strengthened Al-alloy several types of precipitates can form. • At 200 °C, only binary Al–Cu precipitates formed (Al{sub 2}Cu-θ′). • The icosahedral quasicrystalline (IQC) precipitates prevailed at 300 °C. • T-phase (Al{sub 20}Mn{sub 3}Cu{sub 2}) precipitated at temperatures above 400 °C. • The precipitation of different phases did not have a strong effect on hardness.

36 MATERIALS SCIENCE↗

Study of formation mechanism of incipient melting in thixo-cast Al–Si–Cu–Mg alloys

Mechanical properties of thixo-cast Al–Si–Cu–Mg alloys can be enhanced by T61 heat treatment. Copper and magnesium atoms in aluminum matrix can form homogeneously distributed precipitations after solution and aging treatment which harden the alloys. However, microsegregation of these alloying elements could form numerous tiny multi-compound phases during solidification. These phases could cause incipient melting defects in subsequent heat treatment process and degrade the macro-mechanical properties of productions. This study is to present heterogeneous distribution of Cu, Si, and Mg elements and formation of incipient melting defects (pores). In this study, incipient melting pores that occurred during solution treatment at various temperatures, even lower than common melting points of various intermetallic phases, were identified, in terms of a method of investigating the same surface area in the samples before and after solution treatment in a vacuum environment. The results also show that the incipient melting mostly originates at the clusters with fine intermetallic particles while also some at the edge of block-like Al{sub 2}Cu. The fine particles were determined being Al{sub 2}Cu, Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} and Al{sub 8}Mg{sub 3}FeSi{sub 2}. Tendency of the incipient melting decreases with decreases of the width of the clusters. The formation mechanism of incipient melting pores in solution treatment process was discussed using both the Fick law and the LSW theory. Finally, a criterion of solution treatment to avoid incipient melting pores for the thixo-cast alloys is proposed. - Highlights: • In-situ comparison technique was used to analysis the change of eutectic phases. • The ralationship between eutectic phase size and incipient melting was studied. • Teat treatment criterion for higher incipient melting resistance was proposed.

36 MATERIALS SCIENCE↗

3D study of intermetallics and their effect on the corrosion morphology of rheocast aluminium alloy

In the present study, the effect of heat treatment T6.1 on the microstructure and corrosion behaviour of rheocast aluminium alloy A356 is investigated on the basis of 2D/3D characterization techniques and electrochemical and SKPFM measurements. Heat treatment strengthens the α-Al matrix, modifies the intermetallic particles and spheroidizes eutectic Si. These changes do not modify significantly the corrosion behaviour of the alloy. 3D SEM-Tomography clearly shows that the corrosion advances in the shape of narrow paths between closely spaced intermetallics without a major influence of eutectic Si. - Highlights: • T6.1 spheroidizes Si, strengthens the matrix and modifies the intermetallics. • Electrochemical behaviour of untreated and heat-treated alloys is similar. • 3D SEM-Tomography provides additional information on the corrosion morphology. • Corrosion advances as paths between intermetallics with little influence of Si.

36 MATERIALS SCIENCE↗

Cooling thermal parameters and microstructure features of directionally solidified ternary Sn–Bi–(Cu,Ag) solder alloys

Low temperature soldering technology encompasses Sn–Bi based alloys as reference materials for joints since such alloys may be molten at temperatures less than 180 °C. Despite the relatively high strength of these alloys, segregation problems and low ductility are recognized as potential disadvantages. Thus, for low-temperature applications, Bi–Sn eutectic or near-eutectic compositions with or without additions of alloying elements are considered interesting possibilities. In this context, additions of third elements such as Cu and Ag may be an alternative in order to reach sounder solder joints. The length scale of the phases and their proportions are known to be the most important factors affecting the final wear, mechanical and corrosions properties of ternary Sn–Bi–(Cu,Ag) alloys. In spite of this promising outlook, studies emphasizing interrelations of microstructure features and solidification thermal parameters regarding these multicomponent alloys are rare in the literature. In the present investigation Sn–Bi–(Cu,Ag) alloys were directionally solidified (DS) under transient heat flow conditions. A complete characterization is performed including experimental cooling thermal parameters, segregation (XRF), optical and scanning electron microscopies, X-ray diffraction (XRD) and length scale of the microstructural phases. Experimental growth laws relating dendritic spacings to solidification thermal parameters have been proposed with emphasis on the effects of Ag and Cu. The theoretical predictions of the Rappaz-Boettinger model are shown to be slightly above the experimental scatter of secondary dendritic arm spacings for both ternary Sn–Bi–Cu and Sn–Bi–Ag alloys examined. - Highlights: • Dendritic growth prevailed for the ternary Sn–Bi–Cu and Sn–Bi–Ag solder alloys. • Bi precipitates within Sn-rich dendrites were shown to be unevenly distributed. • Morphology and preferential region for the Ag{sub 3}Sn growth depend on Ag content and Ṫ{sub L}. • Rappaz-Boettinger model reasonably estimated the experimental scatter of λ{sub 2}.

36 MATERIALS SCIENCE↗