Martin Seyring

Advance in Orientation Microscopy: Quantitative Analysis of Nanocrystalline Structures

The special properties of nanocrystalline materials are generally accepted to be a consequence of the high density of planar defects (grain and twin boundaries) and their characteristics. However, until now, nanograin structures have not been characterized with similar detail and statistical relevance as coarse-grained materials, due to the lack of an appropriate method. In the present paper, a novel method based on quantitative nanobeam diffraction in transmission electron microscopy (TEM) is presented to determine the misorientation of adjacent nanograins and subgrains. Spatial resolution of <5 nm can be achieved. This method is applicable to characterize orientation relationships in wire, film, and bulk materials with nanocrystalline structures. As a model material, nanocrystalline Cu is used. Several important features of the nanograin structure are discovered utilizing quantitative analysis: the fraction of twin boundaries is substantially higher than that observed in bright-field images in the TEM; small angle grain boundaries are prominent; there is an obvious dependence of the grain boundary characteristics on grain size distribution and mean grain size.

Abnormal crystal structure stability of nanocrystalline Sm2Co17 permanent magnet

Abnormal crystal structure stability is discovered in the single-phase nanocrystalline Sm2Co17 permanent magnet. Three kinds of crystal structures, namely the rhombohedral Th2Zn17-type (2:17 R), the hexagonal TbCu7-type (1:7 H), and the hexagonal Th2Ni17-type (2:17 H), are claimed to exist at room temperature in the Sm2Co17 alloy system. The strong dependence of the magnetic properties on the structure characteristics in the single-phase Sm2Co17 alloy is interpreted in view of the atom space occupancy and the exchange coupling between substructures especially in the nanocrystalline alloy.Abnormal crystal structure stability is discovered in the single-phase nanocrystalline Sm2Co17 permanent magnet. Three kinds of crystal structures, namely the rhombohedral Th2Zn17-type (2:17 R), the hexagonal TbCu7-type (1:7 H), and the hexagonal Th2Ni17-type (2:17 H), are claimed to exist at room temperature in the Sm2Co17 alloy system. The strong dependence of the magnetic properties on the structure characteristics in the single-phase Sm2Co17 alloy is interpreted in view of the atom space occupancy and the exchange coupling between substructures especially in the nanocrystalline alloy.

Nanoscale thermodynamic study on phase transformation in the nanocrystalline Sm2Co17 alloy

The characteristics of phase transformation in nanocrystalline alloys were studied both theoretically and experimentally from the viewpoint of thermodynamics. With a developed thermodynamic model, the dependence of phase stability and phase transformation tendency on the temperature and the nanograin size were calculated for the nanocrystalline Sm(2)Co(17) alloy. It is thermodynamically predicted that the critical grain size for the phase transformation between hexagonal and rhombohedral nanocrystalline Sm(2)Co(17) phases increases with increasing temperature. When the grain size is reduced to below 30 nm, the hexagonal Sm(2)Co(17) phase can stay stable at room temperature, which is a stable phase only at temperatures above 1520 K in the conventional polycrystalline alloys. A series of experiments were performed to investigate the correlation between the phase constitution and the grain structure in the nanocrystalline Sm(2)Co(17) alloy with different grain size levels. The experimental results agree well with the thermodynamic predictions of the grain-size dependence of the room-temperature phase stability. It is proposed that at a given temperature the thermodynamic properties, as well as the phase stability and phase transformation behavior of the nanocrystalline alloys, are modulated by the variation of nanograin size, i.e. the grain size effects on the structure and energy state of the nanograin boundaries.

Characterization of grain structure in nanocrystalline gadolinium by high-resolution transmission electron microscopy

A method is presented for recognition of nanograins in high-resolution transmission electron microscope (HRTEM) images of nanocrystalline materials. We suggest a numerical procedure, which is similar to the experimental dynamic hollow cone darkfield method in transmission electron microscopy and the annular dark-field method in scanning transmission electron microscopy. The numerical routine is based on moving a small mask along a circular path in the Fourier spectrum of a HRTEM image and performing at each angular step an inverse Fourier transform. The procedure extracts the amplitude from the Fourier reconstructions and generates a sum picture that is a real space map of the local amplitude. From this map, it is possible to determine both the size and shape of the nanograins that satisfy the selected Bragg conditions. The possibilities of the method are demonstrated by determining the grain size distribution in gadolinium with ultrafine nanocrystalline grains generated by spark plasma sintering.

The Li–C phase equilibria

Abstract Experimental work using X-ray diffraction and differential scanning calorimetry was conducted on key samples in the Li–C binary system. Reproducible differential scanning calorimetry data with multiple heating cycles were produced only by samples sealed in arc welded Ta-capsules. Only one compound, α/βLi2C2, is found to be stable. A comprehensive Calphad-type assessment was performed and for the first time a consistent thermodynamic description, covering all thermodynamic and phase equilibrium data, is developed. Phase diagrams calculated from that validated database, including the gas phase, are presented. The phase LiC6, was also studied experimentally. It is metastable with respect to α/βLi2C2 + (C), but may be formed from Li + (C). Phase transitions of LiC6, claimed in the literature, are discussed.

A nanocrystalline Sm–Co compound for high-temperature permanent magnets

The inherently high magnetic anisotropy and nanoscale grain size in a Sm5Co19 compound result in an intrinsic coercivity far higher than those of known Sm-Co compounds prior to orientation treatment. The combination of ultrahigh intrinsic coercivity, high Curie temperature and low coercivity temperature coefficient of nanocrystalline Sm5Co19 as a single phase material shows it to be a very promising compound to develop outstanding high-temperature permanent magnets.

ZnO nanoflowers-based photoanodes: aqueous chemical synthesis, microstructure and optical properties

Abstract We have developed an efficient, low temperature, synthetic route for ZnO nanoflowers (NFs) as photoanode material. This alternative route yields small flowerlike nanostructures, built from densely self-assembled tip-ended rod structures. The obtained ZnO NFs possess a large bandgap of 3.27 - 3.39 eV, enabling the generation of an average open current voltage of 0.56 V. Additionally, they show a high internal light harvesting of 14.6•10-7A-mol-1. The growth mechanism and self-assembly of ZnO NFs were studied in detail by joint spectroscopic-TEM investigations. It is shown that the ZnO crystallite size increases with increasing annealing temperatures and that the stress and the improved crystallinity are induced by annealing and reduce the lattice strain and the dislocation density. The bandgaps of ZnO are affected by the lattice strain revealing an optimal region of lattice strain to gain high bandgap energies. The properties of the synthesized ZnO NFs are compared with other morphologies, i.e. ZnO spherical aggregates (SPs) and ZnO nanorods (NRs), and are tested as electrode materials in dye-sensitized solar cells.

Orientation and Phase Analysis of Nanoscale Grains Using Transmission Electron Microscopy

Abstract The nanostructuring of materials is a process which enables their properties to be drastically changed as compared to their coarse crystalline condition. For example, peculiar features were achieved, e.g. extremely high yield and ultimate strengths. The structure of such nanoscale materials has not been characterized yet in detail as compared to materials of a coarser crystalline structure because an appropriate analytical technique did not exist. Nano beam diffraction (NBD) by transmission electron microscopy (TEM) makes possible a local resolution up to 1 nm and, thus, a diffraction analysis of individual nanograins. A recently developed method based on NBD allows determining crystallographic orientation relationships and analyzing the phases of individual nanograins. This article below sets forth the analytical possibilities of this method by way of a complete evidence of twin and small-angle grain boundaries in nanocrystalline copper and a phase identification of precipitates in an AlMg5Si2 alloy.

Materialographic Preparation of Lithium-Carbon Intercalation Compounds

Abstract The materialographic investigation of anode materials for rechargeable lithium ion batteries is a significant step in the understanding and development of electrode materials, but made dramatically more difficult due to the high reactivity of the materials involved. In this work a method is presented which permits the metallographic preparation of the lithium-carbon intercalation compounds used as anode materials in todays rechargeable lithium ion batteries, and which allows the details of their microstructures to be contrasted. After classic, but absolutely water free, preparation in a protective gas atmosphere, the final stage of preparation is carried out using both ion beam polishing and manual polishing on a stationary polishing disc, whereby no significant differences of the quality of the microstructural images obtained is apparent.

Phase formation in alloy-type anode materials in the quaternary system Li–Sn–Si–C

Abstract Investigations on the thermodynamics of alloy-type anode materials have been carried out for the quaternary Li–C–Si–Sn system. Phase equilibria and phase stabilities were characterized in the binary subsystems Li–C, Li–Si, Li–Sn. The Calphad method was first used to optimize or completely re-establish all binary subsystems containing Li. For reasons of consistency, the binary subsystem Si–C had to be revisited and its Calphad description was modified. The ternary phase diagrams were then tentatively calculated by extrapolation from the binary subsystems and confirmed by key experiments. No ternary compounds were found. In order to verify the applicability of the anode materials in real batteries, some of the materials were nanostructured by ball milling and spark plasma sintering, the corresponding nanostructures were characterized. Theoretical predictions that nanograined Li2C2 can also be used as cathode material were verified experimentally. The methodologies worked out in the present project (e. g. nanoscale structure transmission electron microscopy analysis, glow discharge optical emission spectroscopy) were also employed in other projects and led to publications concerning other materials such as Mg alloys, carbon nanofibers and an Mn-based antiperovskite.