Applications of scanning transmission electron microscope microanalysis in the study of materials

The dedicatedstem equipped with field emission electron source, affords opportunities for the acquisition of microchemical and microstructural data on a scale approaching the nanometer level. In this presentation, a number of applications of microchemical analysis and microdiffraction to engineering materials will be discussed, with major emphasis on high-strength low-alloy steels, steels for high formability in automotive applications, and aluminium alloys. Some advantages and limitations of the technique are noted, especially for application to analysis of electrochemically prepared thin foils, and to the analysis of extracted particles.     

Synthesis of nanocrystalline/quasicrystalline Mg32(Al,Zn)49 by melt spinning and mechanical milling

In the present investigation we have made an attempt to synthesize T-Mg₃₂(Al,Zn)₄₉ Frank Kasper phase and investigate the mechanical properties of the T-Phase in micro and nano scale. Single T-Phase (bcc, a = 1.42 nm) has been prepared by conventional casting with a proper combination of flux in order to avoid the loss of magnesium from the melt. Chemical analysis by energy dispersive X-ray microanalysis system attached to scanning electron microscope has confirmed the desired composition for T-phase. The as-cast material was then rapidly solidified by melt spinning and mechanically milled using a high-energy ball mill. The samples were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction techniques. The rapidly solidified foils showed the presence of mostly nanoquasicrystalline phases coexisting with a minute amount of crystalline phases in the thin region where the cooling rate is expected to be high. The dark field imaging in electron microscopy clearly confirms the existence of nano phases. Mechanically milled powder exhibited the evolution of nanophases at higher milling time. Microhardness measurement at low load was carried out in both the as-cast and nanophase materials in order to understand the influence of nanophases on the mode of deformation and cracking at low load.     

Cathodoluminescence from crystalline phases in a ZrO2-SiO2-CeO2 ceramic

The chemical composition of crystalline phases in a ZrO₂-SiO₂-CeO₂ ceramic was determined by electron probe x-ray microanalysis, and the luminescent properties of these phases were studied. The valence state of Ce in these phases was determined from cathodoluminescence data.     

Some aspects of splat-quenching in an inert atmosphere and of the formation of non-crystalline phases in Al-17.3 at. % Cu,germanium and tellurium

An apparatus for splat-quenching by the gun technique in a sealed, inert atmosphere is described. The importance of a low-oxygen quenching atmosphere in promoting efficient spreading of liquid particles and good thermal contact with the quenching surface is shown. A cooling rate of ～10¹⁰ K sec^?1 was estimated from the interlamellar spacing in a quenched Al-17.3 at. % Cu alloy. The process mechanisms of the gun technique are discussed with particular reference to the atomized droplet size and the effective specimen thickness for heat transfer. New non-crystalline phases are reported in electron-transparent areas of splat-quenched foils of Al-17.3 at. % Cu (eutectic composition) pure Ge and pure Te. The glassy Al-Cu phase was also observed in specimens which were chemically thinned from the thicker regions of foils; lattice image studies by high-resolution electron microscopy tentatively suggest that this phase has an amorphous, liquid-like atomic configuration. The peak positions in the electron diffraction patterns of the Ge and Te phases were compared, where possible, with those for the corresponding liquid and vapour-deposited phases. The results for Ge suggest that significant structural rearrangement took place during cooling and freezing from the liquid to give a paracrystalline, tetrahedral short-range order whereas, for Te, the liquid structure was probably largely preserved on freezing.     

Effect of manganese on the oxidation of Fe-Mn-Al-C alloys

The effects of manganese on the oxidation of alloys with the chemical composition (wt%) Fe-5AAl-1.5Mn-0.58C and Fe-5.3Al-3.5Mn-0.53C at 600, 800 and 1000° C in dry air were investigated. Kinetic curves were determined by thermogravimetric analyses. Optical metallography and electron probe microanalysis were used to examine the oxide scales. The kinetic curves of Fe-5.4Al-1.5Mn-0.58C alloy oxidized at 600, 800 and 1000° C had simple, three- and two-stage parabolic rate laws, respectively. On the other hand, two stages of linear rate law were observed in Fe-53Al-3ZMn-0.53C alloy when oxidized at 600° C, while two distinct parabolic rate laws were found in the same alloy oxidized at 800 and 1000° C. Oxidation behaviours and the oxide formation mechanisms of the alloys at different temperatures are discussed in this paper.     

Comparison of transmission electron microscopy and optical microstructures in Al–1% Mg after plane strain compression

Modelling the microstructural evolution of aluminium alloys during hot rolling operations is becoming increasingly dependent on accurate measurements of the deformed microstructure using transmission electron microscopy, scanning electron microscopy and light microscopy. In this paper, an experimental technique which directly compares the microstructure observed in thin foils with that observed using light microscopy is described. This revised version was published online in November 2006 with corrections to the Cover Date.     

Interfacial reactions in the liquid diffusion couples of Mg/Ni,Al/Ni and Al/(Ni)-Al2O3 systems

The interfacial reactions between various molten metals and solid plates were investigated in this diffusion couple study. The molten metals were pure magnesium, pure aluminium, aluminium-rich Al-Mg alloy, and aluminium-rich Al-Cu alloys, and the solid plates were pure nickel plate, alumina plate, and nickel-plated alumina plate. The interfacial reactions in the diffusion couples were determined by using optical microscopy, scanning electron microscopy and electron probe microanalysis in regard to the formation of intermetallic phases, the dissolution rates of the nickel plates, and the morphology of the interfaces. Mg₂Ni phase was found in the pure Mg/Ni plate diffusion couples, and the Al₃Ni and Al₃Ni₂ phases were observed in the pure Al/Ni plate and Al-alloys/Ni plate diffusion couples. In the Al-Cu alloy/Ni-plated alumina plate diffusion couple, Al₂O₃ formed at the interface, while spinel particles were found in the diffusion couples of Al-7.4wt% Mg alloy/Ni-plated alumina plate. Experimental difficulty was encountered in preparing the diffusion couples with alumina plate, and a gap existing at the interface prohibited reactions between the molten metal with alumina plate.     

Electron microscopy of metastable phases in rapidly solidified Al-Co alloys

Four binary Al-Co alloys containing 2·4, 14, 20 and 25 at.% Co and a ternary Al-Co-Si alloy with 20 at.% Co and 5 at.% Si were rapidly solidified from the liquid state by melt spinning. It has been shown that the solid solubility of Co in Al can be increased up to at least 1·7at.% from the negligible value under equilibrium conditions. Two metastable crystalline intermediate phases and a D1 _a -type ordered phase were observed in localized regions in the rapidly solidified Al-2·4at.%Co alloy. A quasicrystalline decagonal phase has been observed in all the other rapidly solidified alloys. This decagonal phase was shown to contain dislocations, dislocation loops and also twin-like defects. The phenomenon of polytypism was also observed in this decagonal quasicrystalline phase. In extremely thin areas of the Al-14at.% Co alloy ribbons on amorphous phase was detected. Transmission electron microscopy was used to extensively characterize the phases in the as-solidified condition and also those produced during and after transformation to the equilibrium constitution. Work carried out when both the authors were in the Department of Metallurgical Engineering, Banaras Hindu University, Varanasi 221 005, India     

Optimization of growth conditions of ZnO nano thin films by chemical double dip technique

Abstract

Zinc oxide (ZnO) nano thin films have been deposited by the chemical double-dip technique using aqueous ZnSO₄ and NaOH solutions. The ZnO films were characterized in terms of surface morphology by x-ray diffraction, energy-dispersive x-ray analysis (EDX), the use of a scanning electron microscope (SEM) and atomic force microscope (AFM) for surface morphology. The films exhibited a smooth morphology. The chemical states of oxygen and zinc in the ZnO nano thin films were also investigated by x-ray photoelectron spectroscopy (XPS). In the present investigations, highly textured ZnO thin films with a preferential (002)-orientation were prepared on glass substrates. The deposition conditions were optimized to obtain device-quality films for practical applications.     

Transformation of the quasicrystalline phase Al-Cr-Fe induced by rapid solidification

A quasicrystalline phase, Q, with icosahedral symmetry was detected by X-ray diffraction and transmission electron microscopy in Al-3Cr-xFe (x=0 1 or 3 at %) alloys elaborated by hot extrusion of rapidly solidified powders. Chemical microanalysis showed the average composition of this phase to be 75 ± 0.5% Al, 12 ± 1%Cr, 12 ± 1% Fe. Annealing treatments led to its transformation into the equilibrium phases Al₁₃Cr₂ and Al₁₃Fe₄, directly at high temperature, or through a metastable and unknown phase, X, at intermediate temperature. This transformation was followed by X-ray diffraction, calorimetry and in situ electron microscopy. The convergent-beam technique was used for characterization of the X phase.     

Improvements in honeycomb abradable seals

Abstract

The concept of utilising honeycomb abradable seals to improve gas turbine engine performance has been under development for many years. Engine operating temperatures, in the region of the seals, have been restricted to below 950°C by the reliance on a chromia scale for degradation protection. The introduction of nickel brazed FeCrAlY based alloys within the honeycomb seal could facilitate a safe increase in operating temperatures to over 1100°C. This is aided by the formation of a more stable, α-alumina scale.

These Fe–20Cr–5Al–0.5Y foils, including the commercially produced variant designated MI2100, have been designed for a service lifetime of up to 24,000 hours. However, burner tests and isothermal oxidation tests in laboratory air at 1100 and 1200°C have shown them to fail after much shorter times. The major degradation of the foils occurs adjacent to the brazed region and limits the lifetime of the honeycomb seal.

Cross-sectional analysis in a scanning electron microscope of seals manufactured from MI2100 foils, after oxidation testing at 1200°C, has shown that voids form beneath the protecting α-alumina scale. In some cases, these voids are filled with silica, with some chromia present, and may be the origin of the subsequent degradation process. The results contrast with tests on free-standing thin foils (100 μm thickness) of MI2100 and other FeCrAlY alloys, where a continuous layer of chromia is formed below the alumina outer scale, once the aluminium content of the alloy drops below a critical composition. Although there is a small amount of silicon in MI2100, the main source of the high level of silicon found in the honeycombs is most likely to be the brazing alloy, since both nickel and silicon from the braze are very mobile in FeCrAlY alloys at high temperatures.

The formation and filling of voids with silica may be associated with the subsequent failure of the protective alumina scales on these brazed alloys, and this mechanism will be developed further in this paper.     

Influence of Processing on the Microstructure of Alloys Which Contain Quasicrystalline Phases

In this investigation a microstructural characterization of the phases obtained in ternary and quaternary alloys was undertaken. One of the main objectives of this study was to explore the possibility of quasicrystalline phases formation under normal casting conditions from the liquid melt. The alloys investigated, were melted in an induction furnace and subsequently cast into a wedge shaped copper mould, which resulted in different cooling velocities in the same ingot. The thick and thin sections of the ingots were characterized by: Optical microscopy, x-ray diffractometry, chemical analysis using EDS and atomic absorption spectroscopy.     

Microstructural characterization of “white zones” in weldable 7000 series alloys

Previous attempts using electron metallographic techniques to study the microstructures of aluminium alloy weldments have been limited by the artefacts introduced by conventional preparation methods such as electropolishing or ion-beam thinning and by difficulties in precisely locating microstructural regions of critical interest in the electron-transparent areas of specimens. This paper describes how microtomy has minimized these problems for the characterization of interfacial regions in AlZnMg alloy weldments that can be susceptible to environment-sensitive fracture. Regions of interest were identified by a linear trace of microhardness indentations on a specimen mechanically polished to a 0.25m finish. This surface was examined in the scanning electron microscope using backscattered electrons to relate the region of interest to specific hardness indentations. Foils for transmission electron microscopy were then microtomed from an area adjacent to the appropriate hardness indentation. Microstructural analysis of the white zone region has been made, using secondary and backscattered electron imaging, transmission electron microscopy, X-ray microanalysis and electron probe microanalysis. The transfer of intermetallics during the welding process to grain boundary regions from intragranular sites, and the segregation of zinc, magnesium and copper (10.0, 3.5 and 0.3 wt% respectively) to grain boundary regions, has been quantified and is briefly discussed with respect to stress corrosion cracking of other AlZnMg (Cu) alloys.     

Physical metallurgy of aluminum-lithium alloys

The addition of lithium to aluminium reduces the density and increases the elastic modulus; precipitation of the metastableδ′(Al₃Li) phase from supersaturated Al-Li solid solution leads to appreciable increase in strength. The enhanced values for specific modulus and specific strength favour the use of the Al-Li alloys as structural materials for aerospace applications. However the binary alloys suffer from problems of poor ductility and toughness associated with strain localisation (resulting from the ease with whichδ′ particles are sheared during deformation), the presence ofδ′-free zones near grain boundaries and the heterogeneous nucleation of the equilibriumδ phase on the grain boundaries. These problems have been overcome by the development of ternary and quaternary alloys containing copper and magnesium. A small amount (∼0·1%) of zirconium is added to these alloys to improve the recrystallisation characteristics. The properties of alloys developed for commercial exploitation are briefly discussed. An overview of the physical metallurgy of the Al-Li alloys is presented with emphasis on the following features: (i) phase equilibria and precipitation reactions in Al-Li, Al-Cu-Mg, Al-Cu-Li and Al-Mg-Li systems and extension of these results to Al-Li-Cu-Mg alloys, (ii) insoluble particles and their effect on precipitation in the alloys, (iii) microstructural studies on Al-2·3%Li-1·2%Cu-0·7%Mg-0·12%Zr alloy, (iv) lithium depletion during solution treatment, (v) coarsening ofδ′ particles and development of precipitate-free zones near grain boundaries and (vi) microanalysis of the lithium containing phases.     

Formation of amorphous Al-Cr alloys by mechanical alloying of elemental aluminium and chromium powders

Mechanical alloying (MA) of elemental aluminium and chromium powders has been performed using a conventional ball-mill. The MA process produces composite metal powders and homogeneously alloyed powders. During continuous heating at the rate of 0.33 K sec^–1 Al-15 at% Cr samples ball-milled for 800 and 1000 h showed two exothermal peaks. The first peak which appeared at the lower temperature corresponds to amorphization of the MA powders. It was confirmed by X-ray and transmission electron microscopy that the heattreated powders, quenched from a temperature just above the first peak, were amorphous phase. Amorphous Al-Cr alloys were formed using elemental powders by MA and subsequent heat treatment.     

Microstructural characterization of two lithium-containing aluminium alloys

The microstructures of two lithium-containing aluminium alloys have been investigated. The two alloys were an Al-Li-Mn alloy, heat treated to provide an under-aged, peak-aged and an over-aged condition, and a commercial Al-Cu-Li alloy, 2020, heat treated and aged to contain ordered precipitate structures. It was observed that both materials were recrystallized with fairly large grains. The Al-Li-Mn material had a high volume fraction of Al₆Mn dispersoids and the Al-Cu-Li alloy had a substantial volume fraction of coarse intermetallic particles and intermediate size disperoids. The major strengthening precipitates were identified from brightfield and dark-field images and selected-area diffraction patterns taken in the transmission electron microscope. Precipitate-free zones were found to be present in both the Al-Li-Mn and Al-Cu-Li alloys. The results of this study suggest that the peak-aged Al-Cu-Li alloy and the under-aged and peak-aged Al-Li-Mn alloys enhance deformation to occur primarily by planar slip, and the larger particle size and interparticle spacing of the over-aged Al-Li-Mn promotes a combination of planar slip and Orowan looping.     

高温熔体反应法制备Al-5Ti-1B细化剂

利用高温熔体反应法成功制备Al-5Ti-1B细化剂。通过热力学计算,确定Al-5Ti-1B细化剂的起始反应温度,研究熔体温度对细化剂组织形貌及吸收率的影响。利用X射线衍射,扫描电子显微镜和X射线能谱仪观察细化剂的相组成和形貌,同时对Al-5Ti-1B细化剂铸锭进行高温挤压,并对挤压出的Ф9.5mm丝材进行微观组织分析和细化实验。结果表明:细化剂主要由TiB_2,TiAl_3,α-Al相组成;850℃制备的细化剂铸锭组织形貌最佳,且Ti和B吸收率达到最佳匹配。挤压后TiAl3相呈细小的块状和TiB_2弥散分布在基体内。添加0.2%(质量分数)细化剂后,纯铝的晶粒尺寸由3.99mm细化到0.45mm。     

Limitations to Accuracy in Extracting Characteristic Line Intensities From X-Ray Spectra

The early development of quantitative electron probe microanalysis, first using crystal spectrometers, then energy dispersive x-ray spectrometers (EDXS), demonstrated that elements could be detected at 0.001 mass fraction level and major concentrations measured within 2 % relative uncertainty. However, during this period of extensive investigation and evaluation, EDXS detectors were not able to detect x rays below 1 keV and all quantitative analysis was performed using a set of reference standards measured on the instrument. Now that EDXS systems are often used without standards and are increasingly being used to analyse elements using lines well below 1 keV, accuracy can be considerably worse than is documented in standard textbooks. Spectrum processing techniques found most applicable to EDXS have now been integrated into total system solutions and can give excellent results on selected samples. However, the same techniques fail in some applications because of a variety of instrumental effects. Prediction of peak shape, width and position for every characteristic line and measurement of background intensity is complicated by variations in response from system to system and with changing count rate. However, with an understanding of the fundamental sources of error, even a total system can be tested like a “black box” in areas where it is most likely to fail and thus establish the degree of confidence that should apply in the intended application. This approach is particularly important when the microanalysis technique is applied at lower electron beam voltages where the extraction of line intensities is complicated by extreme peak overlap and higher background levels.     

The possible transition mechanism for the meta-stable phase in the 7xxx aluminium

Metastable phases in aluminium alloys are the primary nano-scale precipitates which have the biggest contribution to the increase in the tangible mechanical properties. The continuous increase in hardness in the 7xxx aluminium alloys is associated with the phase transformation from clusters or GP-zones to the metastable η′ phase. The high-resolution electron imaging is used to observe the precipitates and reconstruct a kinetic model that might explain the transformation. This work is an attempt to gain insight into how the structural transformation may occur based on the shortest route of diffusion for the eventual structure to result in that of the η′ phase.     

Determination of thicknesses and impurities of targets by measuring backscattered particles from 2 MeV 4He+-bombardment

The measurement of target thicknesses and impurity contents using backscattering, as well as the principle of this technique are briefly described. The targets are irradiated in a beam of 2 MeV ⁴He⁺ ions. The backscattered ions are detected using a Si(Au) solid-state detector. Gold and calcium fluoride on thin carbon backing and selfsupporting silicon foils were determined from peak width measurements. Oxygen and tungsten impurities in a silicon target being prepared by vacuum evaporation from a tungsten boat were determined using the same method. The thickness of a thin aluminium deposit on thick tantalum backing was obtained from the energy shift of the tantalum peak between two spectra recorded with respectively the aluminium and the tantalum facing the ion beam. Copper contamination on the surface on an iron layer electroplated on copper foil was determined by comparison of the copper peak area with the iron peak height in the backscattering spectrum.