HRTEM studies of NiNbZr + Ag amorphous-nanocrystalline composites

Amorphous powder of composition corresponding to Ni60Ti20Zr20 (in at%) was obtained by ball milling in a high-energy mills starting from pure elements. Formation of the amorphous structure was observed already after 20 h of milling, although complete amorphization occurred after 40 h. The microhardness of powders increased from about 30 HV for pure elements to above 400 HV (1290 MPa) after 40 h of milling. Transmission electron microscopy (TEM) allowed to identify nanocrystalline inclusions of intermetallic phases of size 2–10 nm. Uniaxial hot pressing was performed in vacuum at temperature below the crystallization T_x it is 510°C and pressure of 600 MPa, Mixed amorphous powders and nanocrystalline silver powders were used to form a composite, in which microhardness was near 970 MPa HV and 400 HV for the amorphous phase and nanocrystalline silver, respectively. The compression strength of the composite containing 20 wt% of nanocrystalline Ag powder was equal to 600 MPa and plastic strain was 2%. Microstructure studies showed low porosity of composites of less than 1%, uniform distribution of the silver phase and a transition zone between both components, about 150 nm thick, where diffusion of nickel, niobium and zirconium into silver was observed. High-resolution TEM allowed identifying the structure of nanocrystalline inclusions in the amorphous matrix after hot pressing as either Ni₃Zr or Ni₁₇Nb₃. The identification was performed basing on measurements of angles and interatomic distances using inverse Fourier transformed images with enhanced contrast using Digital Micrograph computer program.     

Formation process of β-FeSi2 from amorphous Fe-Si synthesized by ion implantation: Fe concentration dependence

Formation processes of β-FeSi₂ from amorphous Fe-Si layers have been investigated using transmission electron microscopy (TEM). Si(111) substrates were irradiated with 120 keV Fe ions at −150°C to fluences of 1.0 × 10¹⁷ and 4.0 × 10¹⁷ cm^–2. An amorphous Fe-Si layer embedded in an amorphous Si was formed in the low-fluence sample, whereas an amorphous Fe-Si surface layer on an amorphous Si was obtained in the high-fluence one. The amorphous Fe-Si layers were crystallized to β-FeSi₂ after thermal annealing at 800°C for 2 h. Cross-sectional and plan-view TEM observations revealed that, prior to the formation of β-FeSi₂, the amorphous Fe-Si layers crystallized to α-FeSi₂ in the low-fluence sample and to ɛ-FeSi in the high-fluence one. The absence of metastable γ-FeSi₂ which is considered as a precursor of epitaxially grown β-FeSi₂ on Si was attributed to the instability of γ-phase in an amorphous matrix.     

Imaging the three orientation variants of the DO22 phase by 3D atom probe microscopy

Three-phase NiAlV alloys were investigated using a three-dimensional atom probe. Ageing at 800 °C gives rise to the precipitation of two ordered phases within the supersaturated FCC solid solution, namely Ni₃Al (L1₂ structure) and Ni₃V (DO₂₂ structure). The DO₂₂ phase has three orientation variants which need to be identified in 3DAP images. It is shown that an appropriate choice of analysis site enables us to image the chemical order within both L1₂ and DO₂₂ ordered phases and to distinguish the three orientation variants of the DO₂₂ phase in reconstructed images. The lateral resolution of 3DAP in these experimental conditions was estimated through simple considerations to be less than 0.3 nm.     

Structure studies of ball-milled ZrCuAl, NiTiZrCu and melt-spun ZrNiTiCuAl alloys

ZrNiTiCu and ZrNiTiCuAl alloys were amorphized using either a melt‐spinning or ball‐milling process in a high‐energy planetary mill. The elemental powders were initially blended to the desired composition (in at.%) of Zr, 65; Cu, 27.5; Al, 7.5 and of Ti, 25; Zr, 17; Cu, 29; Ni, 29, respectively. The composition of alloys was chosen to be the same as for the bulk amorphous ZrCuAl and easy glass‐forming ZrNiTiCu alloys. An almost fully amorphous structure was obtained after 80 h of milling in the case of both compositions. Transmission electron microscopy studies of ball‐milled powders revealed the presence of nano‐crystallites [2–5 nm for ZrCuAl and smaller (1–3 nm) for the ZrTiNiCu alloy]. High‐resolution transmission electron microscopy of melt‐spun ZrNiTiCuAl ribbons provided evidence of the amorphous structure.     

Precursor effects of martensitic transformations in Ti-based alloys studied by electron microscopy with energy filtering

Precursor effects of martensitic transformations in two well-known shape memory alloys, Ti₅₀Ni₄₈Fe₂ and Ti₅₀Pd₃₄Fe₁₆, were studied extensively by energy-filtered electron microscopy, including in-situ observations, and high-resolution electron microscopy. Energy-filtered dark-field images, where weak diffuse scattering was utilized, clearly showed the microstructure in the premartensitic state of Ti₅₀Ni₄₈Fe₂. Tiny domains observable in this state were close to spherical rather than thin and slender, and the temperature dependence of the domain-like structure was clarified by the in-situ observations. It was found that Ti₅₀Pd₃₄Fe₁₆ exhibited a domain-like structure similar to that of Ti₅₀Ni₄₈Fe₂, which was attributed to a transverse lattice displacement. High-resolution images of Ti₅₀Pd₃₄Fe₁₆ showed that a domain was coupled with other ones with different orientations of distortion, so as to reduce the total strain due to their formations. Furthermore, effects of including a fundamental reflection, in addition to the diffuse scattering, on dark-field images were discussed based on the observations and the image processing.     

Dental gallium alloy composites studied by SEM and TEM

Analytical scanning and transmission electron microscopy (SEM and TEM) studies of dental gallium alloys have been carried out. The Ga alloys were made by triturating a LU powder (Ag–Sn–Cu rich alloy powder) and a GF powder (Ag–Sn–Cu–Pd rich alloy powder) with a liquid Ga alloy containing Ga, In and Sn. The dental materials were found to be composites consisting of remaining, undissolved particles from the Ag-based alloy powders in a matrix of reaction products with the Ga alloy. SEM studies have been carried out to give an overview of the composites. The distribution of the elements was found by the X-ray mapping technique. The phases in the matrix and the remaining alloy particles have been identified by electron diffraction, high-resolution electron microscopy and energy-dispersive X-ray spectroscopy. The following phases were identified in the LU alloy: orthorhombic Ag₃Sn, cubic Ag₉In₄, tetragonal β-Sn and hexagonal Ag₂Ga. In addition to these well-known phases Ga-rich regions were observed consisting of an intergrowth of tetragonal CuGa₂ and one of the cubic γ-Cu₉Ga₄ phases. In addition to these phases cubic Ga₇Pd₃ was found in the GF alloy. The anomalous setting expansion of the GF alloy may be explained by the presence of Ga₇Pd₃.     

Preparation and characterization of nanocrystalline ZrO2-7%Y2O3 powders for thermal barrier coatings by high-energy ball milling

High-energy ball milling is an effective method to produce nanocrystalline oxides. In this study, a conventional ZrO₂-7%Y₂O₃ spray powder was ball-milled to produce nanocrystalline powders with high levels of crystalline disorders for deposition of thermal barrier coatings. The powder was milled both with 100Cr6 steel balls and with ZrO₂-3%Y₂O₃ ceramic balls as grinding media. The milling time was varied in order to investigate the effect of the milling time on the crystallite size. The powders were investigated in terms of their crystallite sizes and morphologies by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that under given milling conditions the powder was already nanostructured after 40 min milling. The crystallite size decreased significantly with increasing milling time within first 120 min. After that, a further increase of milling time did not lead to a significant reduction of the crystallite size. Ball-milling led to lattice microstrains. Milling with the steel balls resulted in finer nano-sized crystal grains, but caused the contamination of the powder. The nano-sized crystal grains coarsened during the heat-treatment at 1250°C.     

Accurate structure determinations of very small (4–20 nm) areas, using refinement of dynamic electron diffraction data

It is shown that accurate structure refinements are possible from electron diffraction data obtained using areas 4–20 nm in diameter and 4–20 nm thick. To obtain accurate atomic positions it is essential to take the dynamic diffraction fully into account, for which new software was developed. Examples (La₃Ni₂B₂N₃, Ba₂Ca₃Cu₅O_10+δ and Ce₅Cu₁₉P₁₂) are given of the structure refinements of known and unknown structures with R -values in the range 2–6%. The procedure reported in this paper opens the way to structure determination of particles in many materials of industrial and scientific interest which cannot be solved by conventional structure determination (e.g. because of small size, heavily twinned materials or small fractions in polyphase materials).     

Estimation of average particle size from vertical projections

A new stereological relationship is derived for the estimation of average size (average width) of a collection of convex particles in a 3D microstructure. The average size is estimated from measurements performed on projected images of the microstructure generated by total vertical projections. The stereological relationship is as follows: D = Ī _C /(2 N ₀β). D is the average width, ¯ I _C is the average absolute number of intersections between the specifically oriented and regularly spaced cycloid shape test lines and particle boundaries observed in the total vertical projections, N ₀ is the total number of particles observed in the total vertical projection and the parameter β is a characteristic of the measurement grid; it has units of reciprocal of length. The result is applicable to any arbitrary collection of convex particles; the particle orientations need not be isotropic. Only 'intersection counts' are required; it is not necessary to measure sizes of the particles in the projected images.     

Characterization of cast Al86Mn3Be11 alloy

An Al₈₆Mn₃Be₁₁ alloy cast into copper mould was subjected to metallographic investigation. The as-cast microstructure consisted of a quasicrystalline icosahedral phase (i-phase), Be₄AlMn phase and, occasionally, a hexagonal phase. Al-rich solid solution represented the dominant phase. The chemical compositions of phases were determined using AES. The composition of the Be₄AlMn slightly deviated from the stoichiometric composition, whereas the composition of the i-phase was approximately Al₅₂Mn₁₈Be₃₀, containing an appreciable amount of Be. The average composition of the hexagonal phase was Al₆₆Mn₂₁Be₁₃. Deep etching and particle extraction provided a deep insight into the three-dimensional morphology of the i-phase and the hexagonal phase, whereas Be₄AlMn was slightly attacked by the etchant. The i-phase was present predominantly in the form of dendrites and a rodlike eutectic phase. The hexagonal phase was primarily in the form of hexagonal platelets, whereas Be₄AlMn was rather irregular in shape. The morphology of the i-phase can be explained by predominant growth in 3-fold directions and the lowest energy of the 5-fold planes, leading to the faceting and adopting a pentagonal dodecahedron shape. The brightnesses of phases in the backscattered electron images were rationalized by determining their backscattering coefficients. TEM investigation showed considerable phason strain in the i-phase, and the polycrystalline nature of the Be₄AlMn phase.     

Structural studies of pulsed-laser deposited nanocomposite metal-oxide films

Pulsed laser deposition in vacuum has been used to develop metal-oxide nanocomposite films with well controlled structural quality. Results for the copper–aluminium oxide (Cu:Al₂O₃) system are used to illustrate the main morphological and structural features of these films. High resolution transmission electron microscopy (TEM) analysis shows that the films consist of Cu nanocrystals with average dimensions that can be controlled between 2 nm and 10 nm embedded in an amorphous Al₂O₃ matrix. It is observed that the in-plane shape of the nanocrystals evolves from circular to elongated, and the number of nanocrystals per unit area decreases as their size increases. This evolution is explained in terms of nucleation at the substrate surface and coalescence during the later stages of growth. The thermal stability of the films has been studied by in situ TEM annealing and no transformation could be observed up to about 800 °C when partial crystallization of the Al₂O₃ starts.     

A study of the initial growth of PtxCo(1−x) thin films on Si3N4

Pt _x Co_{(1− x )} thin films where x  =0.24 have been deposited onto Si₃N₄ windows and studied using transmission electron microscopy. The films are used in ultrahigh-density recording studies and it was found that the surface of the substrate had a strong influence on the microstructure, crystallography and magnetic properties of the film. An investigation of the early growth of the film was made by studying films of different thickness between 100 and 300 Å. It was found that the grains were hexagonal in structure with a strong c -axis orientation perpendicular to the surface.     

Transmission electron microscopy studies of microstructure of Ti–Nb and Ti–Ta alloys after ball milling and hot consolidation

Two Ti alloys with compositions Ti?10Ta and Ti?10Nb (at.%) were milled in a high‐energy mill for a maximum of 80 h in an argon atmosphere. A nanocrystalline structure of α‐Ti(X) (X = Ta or Nb) solid solution was formed in both investigated alloys after milling, as shown by X‐ray diffraction. Transmission electron microscopy observations of powders milled for 80 h revealed chemical inhomogeneity of particles in nanometre‐scale regions and an average crystallite size of about 10 nm. The pulse plasma sintering method was applied for hot consolidation of milled powders. The mean density of pulse plasma sintering compacts of Ti–Nb alloy was about 99.5% of the theoretical value, whereas the density of the Ti?10Ta sample was lower, close to 92% of the theoretical value. Transmission electron microscopy observation of compacted samples showed that the sintering process caused the formation of a two‐phase α + β structure in both investigated alloys, with a mean grain size of 220 nm. The chemical inhomogeneity and high degree of deformation in nanometre‐scale regions of milled powders led to a martensitic transformation, resulting in formation of a 9R martensite structure.     

The use of amphipathic polymers for cryo electron microscopy of NADH:ubiquinone oxidoreductase (complex I)

Atom removal from surfaces via bombardment by ion beams – ion beam sputtering or ion milling – is a widely employed technique to form geometric structures in materials. In this work we present and test a new method to achieving uniform material removal from an irregular surface. The method is based on ion milling at off-normal incidence under four consecutive perpendicular azimuthal specimen orientations. Mathematical analysis shows that uniform ion milling of an uneven surface is achieved at the polar angle of incidence θ where the quantity     has its maximum [ Y (θ) is the number of removed atoms per incident ion].
The four-azimuth milling procedure is tested successfully for a 30 keV Ga⁺ beam on a suspended but wrinkled Si₃N₄/Au bilayer foil and on truncated Si pyramids with slopes up to 40°. Despite the variations in local surface orientations, uniform milling is achieved at a polar incidence angle of 45° and four consecutive azimuths of 0°, 90°, 180° and 270°.     

Structure of electrodeposited graded composite coatings of Ni–Al–Al2O3

The structure of electrodeposited composite coatings of Ni–Al–Al₂O₃, with Ni as the matrix and Al and Al₂O₃ as second-phase particles, was investigated using light microscopy and scanning electron microscopy. Ni coatings with no particles, which were used as reference samples, had progressively coarser structures with increasing current density. Co-deposition with Al resulted in refinement of the Ni matrix structure at high (>10 A dm⁻²) current densities. For single-particle baths, the co-deposition of Al₂O₃ was more strongly affected by current density and bath particle content than was the co-deposition of Al. However, for baths containing both Al and Al₂O₃ the amount of incorporated Al₂O₃ no longer depended on current density. With the choice of appropriate conditions, coatings of Ni with up to 39 vol.% Al₂O₃ were made. Similar experiments with Al yielded a maximum of 17.5 vol.% only. Uniform and graded mixed-particle coatings were also produced. When coatings containing Al were annealed, the reaction of the two elements resulted in the formation of either single-phase γ or two-phase γ–γ' alloys, in agreement with the equilibrium phase diagram.     

Tb2TiO5-Dy2TiO5中子吸收材料的显微组织及性能

以Tb₄O₇粉、Dy₂O₃粉和TiO₂粉为原料,采用高能球磨、冷等静压和高温烧结工艺制备了Tb₂TiO₅-30%(质量分数)Dy₂TiO₅中子吸收材料,研究不同球磨时间(0~48 h)下混合粉体的微观结构,不同烧结温度(1 200~1 400℃)与时间(1~96 h)下烧结块体材料的微观结构、热物理性能和耐腐蚀性能。结果表明:混合粉体的晶粒尺寸随球磨时间的延长而减小,球磨12 h后即可获得均匀混合的纳米晶粉体,纳米晶混合粉体在1 300℃烧结96 h获得了具有高致密度正交晶体结构Tb₂TiO₅-Dy₂TiO₅块体材料;该块体材料在500℃的热导率和热膨胀系数分别为2.2 W·m^-1·K^-1和5.8×10^-6 K^-1,在360℃/18.6 MPa去离子水中的腐蚀速率变化很小,平均腐蚀速率为0.18 mg·dm^-2·h^-1,该块体材料具有较高的热导率、较低的热膨胀系数以及较好的耐高温水腐蚀性能,是控制棒用中子吸收材料较优的候选材料。     

Transmission electron microscopy studies of squeeze cast Al-AlN composites

Aluminium-matrix composites containing ∼45 vol.% AlN particles were fabricated by melt infiltration of aluminium into an AlN preform under a pressure up to 130 MPa. Three types of aluminium alloy (2024, 6060 and 5754) were used. The as-prepared composites were studied by light microscopy, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. As a result of the melt infiltration process, the composites are very dense and the microstructure shows a homogeneous distribution of the reinforcement. The interfaces are clean with very little porosity. Composites with 2024 and 6060 matrices were carefully studied by transmission electron microscopy (TEM) and high resolution electron microscopy (HREM) after heat treatments. Dislocation density in the matrix of the reinforced material increases due to the difference in thermal expansion coefficients of aluminium alloys and AlN. This can induce an accelerated ageing response of the coherent and semicoherent precipitations of age-hardened matrices. This behaviour has been studied in the 2024 and 6060 composites by using microhardness measurements and TEM. Reactions between the AlN reinforcement and aluminium matrices (6060 and 5754) were observed and analysed by TEM. Matrices containing some of magnesium display a MgAl₂O₄ spinel formation at the AlN/matrix interface. The spinel formation is probably due to the reaction between magnesium of the matrix and the thin Al₂O₃ layer on the AlN surfaces. This reaction can affect the mechanical behaviour of the composite infiltrated with the 5754 matrix. This has been confirmed by overageing some samples at high temperatures (300 °C and 550 °C) for 10 days in order to emphasize the interfacial reactions.     

Development of an optimal protocol for the ultrastructural examination of skin by transmission electron microscopy

The intercellular lipid bilayers of the stratum corneum provide the permeability barrier of the skin. To perform an electron microscopical examination of the ultrastructure of these bilayers, ruthenium tetroxide fixation is required. In this study an optimal fixation protocol was developed and selected upon comparing seven different fixation procedures, using glutaraldehyde (GA) and the postfixatives ruthenium red, osmium tetroxide (OsO₄) and ruthenium tetroxide (RuO₄) in combination with potassium ferrocyanide (K₄Fe(CN)₆) and potassium ferricyanide (K₃Fe(CN)₆). Instead of fixing skin with either OsO₄ or RuO₄, these two fixatives were combined in one protocol. In addition, the use of RuRed was introduced and the influence of both K₄Fe(CN)₆ and K₃Fe(CN)₆ in combination with RuO₄ were examined. Furthermore, we compared two dehydration solvents, methanol and acetone.
The most satisfying results were obtained when the skin was prefixed in GA and postfixed in OsO₄ and RuO₄ with K₃Fe(CN)₆, i.e. with Fe in its highest oxidation state (Fe³⁺). No differences were observed between dehydration in methanol and acetone.     

Preparation of ultrafine α-AlO using precipitation-azeotropic distillation method

Ammonium aluminum carbonate hydroxide (AACH) was prepared by a precipitation-azeotropic distillation method, which uses aluminum sulfate as the Al source and ammonium carbonate as the precipitant. Then, AACH was calcined into ultrafine ?-Al₂O₃ powder. The factors that influence the dispersion property of ultrafine ?-Al₂O₃ powder are discussed in this paper, such as the methods of adding materials, surfactant, and drying methods. The changes of the structure and property of ultrafine alumina in the thermal treatment process are also studied. The morphological structure and properties of AACH are characterized by DTA/TGA, SEM, XRD, and ICP measurements. The results show that ultrafine ?-Al₂O₃ powder with a uniform particle size and well-distributed property can be synthesized only after aluminum sulfate atomizes into ammonium carbonate, proper amount of PEG1000 is added as the dispersant, and the product is treated by azeotropic distillation. The phase transformation of alumina during the calcination process can be described as amorphous Al₂O₃ → ?-Al₂O₃ → ?-Al₂O₃ → ?-Al₂O₃. The crystal grain size and density of ultrafine alumina powder increase with the increase of the calcination temperature. After AACH has been calcined at 1200°C for 2 h, the ultrafine ?-Al₂O₃ with uniform particle size, spherical shape, and more than 99.97% purity is obtained and its powder is well dispersed.     

A nanometre-scale non-periodic structural variation in high temperature superconducting ceramics and the implications for properties

Non-periodic structural variation has been found in the high T _c cuprates, YBa₂Cu₃O_{7- x} and Hg_0.67Pb_0.33Ba₂Ca₂Cu₃O_8+δ, by image analysis of high resolution transmission electron microscope (HRTEM) images. We use two methods for analysis of the HRTEM images. The first method is a means for measuring the bending of lattice fringes at twin planes. The second method is a low-pass filter technique which enhances information contained by diffuse-scattered electrons and reveals what appears to be an interference effect between domains of differing lattice parameter in the top and bottom of the thin foil. We believe that these methods of image analysis could be usefully applied to the many thousands of HRTEM images that have been collected by other workers in the high temperature superconductor field. This work provides direct structural evidence for phase separation in high T _c cuprates, and gives support to recent stripes models that have been proposed to explain various angle resolved photoelectron spectroscopy and nuclear magnetic resonance data. We believe that the structural variation is a response to an opening of an electronic solubility gap where holes are not uniformly distributed in the material but are confined to metallic stripes. Optimum doping may occur as a consequence of the diffuse boundaries between stripes which arise from spinodal decomposition. Theoretical ideas about the high T _c cuprates which treat the cuprates as homogeneous may need to be modified in order to take account of this type of structural variation.