Comparison of Segregation Behaviors for Special and General Boundaries in Polycrystalline Al2O3 with SiO2-TiO2 Impurities

A systematic study of grain boundaries with an elongated grain morphology in TiO₂-doped polycrystalline Al₂O₃ materials with SiO₂ impurities is reported in this paper. Over 20 grain boundaries, all having common (0001) basal plane surface on one side, were investigated by using HRTEM and analytical TEM. A few of them were basal plane twin boundaries or other non-wetting boundaries, and the majority of grain boundaries were covered by amorphous phases, either as continuous films or with small pockets bounded by surface facets. Si and Ti were segregated to all boundaries, however, two categories of segregation were observed. Excesses of both segregants were between 1.0–4.0 atom/nm² at special and non-wetting boundaries, while they were in the range of 7.0–30 atom/nm² at boundaries with amorphous phases. A variation of amorphous film thickness was also observed, which has a clear relation with Si excess level while Ti excess remained at the same level. This observation suggests that the amorphous phases were primarily made of SiO₂ but Ti segregants were attached to grain surfaces. The variation in thickness of SiO₂-based film is strongly related to the surface structure of anisotropic Al₂O₃ grains.     

AES/STEM grain boundary analysis of stabilized zirconia ceramics

Semiquantitative Auger Electron Spectroscopy (AES) on pure monophasic (ZrO₂)_0.83(YO_1.5)_0.17 was used to determine the chemical composition of the grain boundaries. Grain boundary enrichment with Y was observed with an enrichment factor of about 1.5. The difference in activation energy of the ionic conductivity of the grain boundary compared with the bulk can be explained by the Y segregation.When Bi₂O₃ is introduced into this material and second phase appears along the grain boundaries of the cubic main phase. Energy dispersive X-ray analysis (EDS) on a scanning transmission electron microscope (STEM) shows an enrichment of bismuth at the grain boundaries of this second phase.     

晶界在多晶ZrO2基固体电解质中的作用

在实验的基础上将ZrO₂基固体电解质的晶界分为三类:“清洁”晶界、含非晶相的晶界和含晶态相晶界,并分析了各类晶界的形态与性质,其中根据有效介质理论的计算,晶态晶界相的电导率约为基体的三倍,因而据此提出了一个运用“晶界工程”进一步提高ZrO₂导电性的方法。用理论模型分析了各类晶界对ZrO₂氧传感器输出电势的影响。 关键词：     

Grain Boundaries in Barium Strontium Titanate Thin Films: Structure, Chemistry and Influence on Electronic Properties

In this paper, we investigate the role of grain boundaries in polycrystalline (Ba _x Sr_1–x )Ti_1+y O_3+z films, grown by metal organic vapor deposition, in the accommodation of nonstoichiometry, as well as their role in the strong composition dependence of the electric and dielectric behavior observed in these films. High-spatial resolution electron energy-loss spectroscopy is used for the analysis of composition and structural changes at grain boundaries, as a function of film composition. The existence of amorphous, titanium rich, TiO₂-like phases at the grain boundaries of films with large amounts of excess Ti (y 0.08) may explain the non-monotonic resistance degradation behavior of the films as a function of Ti content. However, we show that a grain boundary phase model fails to explain the strong composition dependence of the dielectric behavior. Electron energy-loss spectra indicate a distortion of the Ti–O octahedra in the grain interiors in samples with increasing Ti excess. The decrease of the dielectric constant with increasing amounts of excess Ti is therefore more likely due to Ti accommodation in the grain interiors.     

Electron beam-physical vapor deposition of SiC/SiO2 high emissivity thin film

When heated by high-energy electron beam (EB), SiC can decompose into C and Si vapor. Subsequently, Si vapor reacts with metal oxide thin film on substrate surface and formats dense SiO₂ thin film at high substrate temperature. By means of the two reactions, SiC/SiO₂ composite thin film was prepared on the pre-oxidized 316 stainless steel (SS) substrate by electron beam-physical vapor deposition (EB-PVD) only using β-SiC target at 1000 °C. The thin film was examined by energy dispersive spectroscopy (EDS), grazing incidence X-ray asymmetry diffraction (GIAXD), scanning electron microscopy (SEM), atomic force microscopy (AFM), backscattered electron image (BSE), electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS) and Fourier transformed infra-red (FT-IR) spectroscopy. The analysis results show that the thin film is mainly composed of imperfect nano-crystalline phases of 3C-SiC and SiO₂, especially, SiO₂ phase is nearly amorphous. Moreover, the smooth and dense thin film surface consists of nano-sized particles, and the interface between SiC/SiO₂ composite thin film and SS substrate is perfect. At last, the emissivity of SS substrate is improved by the SiC/SiO₂ composite thin film.     

Distribution of oxygen vacancies and gadolinium dopants in ZrO2–CeO2 multi-layer films grown on α-Al2O3

Gdolinia doped ZrO₂ and CeO₂ multi-layer films were deposited on α-Al₂O₃ (0001) using oxygen-plasma-assisted molecular-beam epitaxy. Oxygen vacancies and Gd dopant distributions were investigated in these multi-layer films using X-ray diffraction (XRD), conventional and high-resolution transmission electron microscopy (HRTEM), annular dark-field imaging in scanning transmission electron microscopy (STEM), X-ray energy dispersive spectroscopy (EDS) elemental mapping and X-ray photoelectron spectroscopy (XPS) depth profiling. EDS and XPS depth profiling reveal that the Gd concentration in the ZrO₂ layer is lower than that in the CeO₂ layer. As a result, a higher oxygen vacancy concentration exists in the CeO₂ layers compared to that in the ZrO₂ layers. In addition, Gd is found to segregate only at the interfaces formed during the deposition of CeO₂ layers on ZrO₂ layers. On the other hand, the interfaces formed during the deposition of ZrO₂ layers on CeO₂ layers did not show any Gd segregation. The Gd segregation behavior at every other interface is believed to be associated with the low solubility of Gd in ZrO₂.     

SEM and TEM analysis of composite of ZrO2-Ti system

3Y-ZrO₂-Ti composites obtained by slip casting method were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Moreover, the Vickers hardness was measured. The experiments show the complex microstructure of composites. The tetragonal zirconium dioxide (t-ZrO₂) and monoclinic zirconium dioxide (m-ZrO₂) as a composite matrix were detected at XRD analysis. SEM observations revealed that Ti -rich phase are uniform distributed in composites. Moreover, the large and very fine precipitations were found. The very fine Ti rich precipitations were located at ZrO₂ grain boundaries as well as in the triple-points. TEM experiments confirmed that in the sintered composites 3Y-ZrO₂ – 10%Ti the uniaxial ZrO₂ grains (100–600 nm), fine monoclinic martensitic plates and fine round monoclinic particles (20–40 nm) of ZrTiO₂ phase were exist. The complex microstructures of 3Y-ZrO₂-Ti composites have a high hardness as a result of existing fine ZrTiO₂ and other Ti oxides precipitations.     

Morphology and microstructure of all-epitaxial ferroelectric tri-layered (Bi,La)4Ti3O12/Pb(Zr0.4Ti0.6)O3/ (Bi,La)4Ti3O12 thin films on SrTiO3(011)

The morphology and microstructure of all-epitaxial (Bi,La)₄Ti₃O₁₂/Pb(Zr_0.4Ti_0.6)O₃/(Bi,La)₄Ti₃O₁₂ (BLT/PZT/BLT) tri-layered ferroelectric films, grown on (011)-oriented SrTiO₃ (STO) substrates by pulsed laser deposition, are investigated by transmission electron microscopy (TEM). X-ray diffraction and electron diffraction patterns demonstrate that the epitaxial relationship between BLT, PZT and STO can be described as ; . Cross-sectional TEM images show that the growth rate of BLT is nearly two times that for PZT at the same growth conditions, and 90° ferroelectric domain boundaries lying on {110} planes are observed in the PZT layer. The 90° ferroelectric domains in the PZT layer extend up to 600 nm in length. Long domains penetrate into the neighboring columnar grain through the columnar grain boundary, whereas others are nucleating at the columnar grain boundaries. The roughness of the PZT/BLT interfaces appears to depend on the viewing direction, i.e., it is different for different azimuthal directions. Planar TEM investigations show that the grains in the top BLT layer have a rod-like morphology, preferentially growing along the [110]_BLT direction. The grain width is rather constant at about 90 nm, whereas the length of the grains varies from 150 to 625 nm. These morphological details point to the important role the crystal anisotropy of BLT plays for the growth and structure of the tri-layered films. PACS 81.15-z; 68.37.Lp; 77.84.-s     

Hydrogen solubility in amorphous Mg<Subscript>0.6</Subscript>SiO<Subscript>2.6</Subscript> at high pressure

The solubility of hydrogen in amorphous Mg_0.6SiO_2.6 at a temperature of 250°C and pressures up to 75 kbar is studied using a quenching technique. The molar ratio H₂/formula unit is found to nonlinearly increase with pressure from x = 0.12 at P = 10 kbar to x = 0.303 at P = 75 kbar. An investigation of the quenched samples by Raman spectroscopy demonstrated that hydrogen dissolves in amorphous Mg_0.6SiO_2.6 in the form of H₂ molecules. X-ray diffraction and Raman studies showed that the hydrogenation of the samples is likely to be accompanied by a phase transition in the amorphous lattice of Mg_0.6SiO_2.6 at P ≈ 52.5 kbar to a denser amorphous modification.     

Study on preparation and properties of molybdenum alloys reinforced by nano-sized ZrO<Subscript>2</Subscript> particles

The nano-sized ZrO₂-reinforced Mo alloy was prepared by a hydrothermal method and a subsequent powder metallurgy process. During the hydrothermal process, the nano-sized ZrO₂ particles were added into the Mo powder via the hydrothermal synthesis. The grain size of Mo powder decreases obviously with the addition of ZrO₂ particles, and the fine-grain sintered structure is obtained correspondingly due to hereditation. In addition to a few of nano-sized ZrO₂ particles in grain boundaries or sub-boundaries, most are dispersed in grains. The tensile strength and yield strength have been increased by 32.33 and 53.76 %.     

Grain boundaries in the refined solidification structure of undercooled Ni75Pd25

When a single-phase alloy solidifies in a low-undercooling range or above a critical undercooling, grain-refined structures are obtained. Taking Ni₇₅Pd₂₅ alloy as an example, the microscopic orientation of the refined grains was investigated by electron backscattered diffraction technology. It is revealed that the refined grains at low undercooling are completely randomly distributed. In the refined structure at high undercooling, certain grain boundaries with misorientation angles less than 5° can be observed, while most of the grain boundaries have large misorientation angles. The inverse pole figure indicates that the refined grains at high undercooling have a textured crystallographic orientation. The fact that twins exist in the refined structure at high undercooling and the dendritic substructure arms exhibit no misorientation supports such an argument that the grain refinement at high undercooling results from the recrystallization of the solidification dendrites.     

Microstructure and thermal stability of Fe,Ti, and Ag implanted yttria-stabilized zirconia

Yttria-stabilized zirconia (YSZ) was implanted with 15 keV Fe or Ti ions up to a dose of 8×10¹⁶ at cm^–2. The resulting dopant concentrations exceeded the concentrations corresponding to the equilibrium solid solubility of Fe₂O₃ or TiO₂ in YSZ. During oxidation in air at 400° C, the Fe and Ti concentration in the outermost surface layer increased even further until a surface layer was formed of mainly Fe₂O₃ and TiO₂, as shown by XPS and ISS measurements. From the time dependence of the Fe and Ti depth profiles during anneal treatments, diffusion coefficients were calculated. From those values it was estimated that the maximum temperature at which the Fe- and Ti-implanted layers can be operated without changes in the dopant concentration profiles was 700 and 800° C, respectively. The high-dose implanted layer was completely amorphous even after annealing up to 1100° C, as shown by scanning transmission electron microscopy. Preliminary measurements on 50 keV Ag implanted YSZ indicate that in this case the amorphous layer recrystallizes into fine grained cubic YSZ at a temperature of about 1000° C. The average grain diameter was estimated at 20 nm, whereas the original grain size of YSZ before implantation was 400 nm. This result implies that the grain size in the surface of a ceramic material can be decreased by ion beam amorphisation and subsequent recrystallisation at elevated temperatures.     

Multiscale model of deformed polycrystals. Hall-Petch problem

The paper puts forward a multiscale model of deformed polycrystals according to which the basis for self-consistent deformation of grains is rotational wave flows of planar structural transformations at their boundaries. Computer-aided engineering of grain boundaries reveals two types of rotational wave flows defined by the misorientation angle of adjacent grains. Grain boundary flows of the first type develop at low-angle boundaries and feature low curvature. These flows generate dislocations in the grain bulk and the Hall-Petch equation for them has the form σ=σ₀+kd^?1/2. Grain boundary flows of the second type develop at high-angle boundaries and feature high curvature. These flows generate curvature bands in near-boundary zones and inject them into the grain bulk, resulting in fragmentation of grains and breakdown of translation invariance. For such self-consistency of grains in a polycrystal, the Hall-Petch equation has the form σ=σ₀+kd^?1. Experimental data in support of the proposed multiscale model are presented.     

Microstructure of aluminium-copper thin films and its relation to electromigration

The microstructure of polycrystalline aluminium — 7·6 wt % copper thin films evaporated from the starting Al-Cu alloy was studied using electron microscopy and microanalysis. The structural properties of films were confronted with electromigration lifetime measurements of Al-Cu thin film conductors. In the films Al₂Cu precipitates were observed. Thermodynamically stable -Al₂Cu precipitates were found at grain boundaries, triple points and on the film surface. Within the grains -Al₂Cu precipitates were detected. When the temperature of deposition and/or the time of annealing of the films at 480 °C in nitrogen increased, the growth of grains and of the total volume of the precipitate phase was observed. Under these conditions precipitates tended to grow preferentially at the film surface and they ceased to influence the grain size distribution. The distribution approached then the log-normal distribution function. With regard to the structural investigations it is anticipated that the best electromigration resistance among the studied samples should possess conductors deposited at 250 °C as well as conductors deposited at 150 °C and 250 °C and annealed 10 min at 480 °C. The lifetimes of conductors having this type of microstructure and tested at the current density of 3×10⁶ A/cm² had values of 210÷3500 hrs, corresponding to the testing temperature of 150 °C. Higher lifetimes were observed with wider (20 m) and shortest (120 m) conductors encapsulated in packages filled with nitrogen. The activation energy for the failure process was 0·65 eV in this case.     

The Electronic Structure of Pristine and Doped (100) Tilt Grain Boundaries in SrTiO3

To understand the electronic properties of doped grain boundaries, we reviewed the atomic scale techniques currently available to study the electronic structure at pristine SrTiO₃ grain boundaries. The knowledge gained from the pristine boundaries is used to interpret experimental and theoretical results from a Mn doped 5 SrTiO₃ grain boundaries. Mn atoms are shown to preferentially substitute at specific Ti sites at the grain boundary core. Furthermore, the formal oxidation state of the Mn atoms at the grain boundary core was found to be reduced compared to the Mn atoms substituting for Ti in the bulk. This change of valence did not, however, significantly affect the atomic structure of the grain boundary, as determined by Z-contrast imaging and electron energy-loss spectroscopy, which revealed similar fine-structure features at both the doped and pristine grain boundary. We conclude, therefore, that composition and atomic structure have different effects on the local electronic structure and should be treated separately in any segregation and electrical conductivity models for grain boundaries.     

Playback performance and microstructure of sputtered tape media formed by facing targets sputtering

Sputtered tape media of a CoPtCr–SiO₂ magnetic layer with a Ru underlayer was fabricated on a thin Aramid film by a facing targets sputtering (FTS) system at room temperature with no cooling. Transition electron microscope (TEM) images show columnar epitaxial growth of hcp-CoPtCr(1 0 0) plane on hcp-Ru(1 0 0). Average grain diameter of 10.2 nm with dispersion of 20.2% was obtained from TEM images. Enrichment of Co and Pt inside grains and segregation of Cr and Si to boundary were confirmed by point energy dispersive spectroscopy (EDS) measurements. Playback performance test on sputtered sample indicated that SNR is higher and PW50 value is lower than that of commercial coated tapes. These good playback properties could come from fine and isolated grain structure of magnetic layer of sputtered sample, as observed by TEM.     

Femtosecond laser-induced damage in reflector

We have investigated the damage for ZrO₂/SiO₂ 800 nm 45° high-reflection mirror with femtosecond pulses. The damage morphologies and the evolution of ablation crater depths with laser fluences are dramatically different from that with pulse longer than a few tens of picoseconds. The ablation in multilayers occurs layer by layer, and not continuously as in the case of bulk single crystalline or amorphous materials. The weak point in damage is the interface between two layers. We also report its single-short damage thresholds for pulse durations ranging from 50 to 900 fs, which departs from the diffusion-dominated scaling. A developed avalanche model, including the production of conduction band electrons (CBE) and laser energy deposition, is applied to study the damage mechanisms. The theoretical results agree well with our measurements.     

Effect of alumina addition on the microstructure and grain boundary resistance of magnesia partially-stabilized zirconia

The electrical properties of 9 mol% MgO–ZrO₂ (Mg-PSZ) with 1 mol% Al₂O₃ and the mechanisms for electrical degradation were investigated using structural, morphological, and electrochemical analyses. The addition of Al₂O₃ caused an increase in both the monoclinic and the Mg-rich phases at the grain boundaries in the Mg-PSZ. Coarse grains larger than 20 μm and an intergranular layer composed of the Mg-rich phase were identified in a specimen sintered at 1600 °C. This specimen exhibited a minimum of ionic conductivity (4.98 × 10⁻⁴ S cm⁻¹ at 700 °C) due to the grain boundary resistance (245 Ω cm²), which dominated the overall resistance. A similar trend was observed over the entire temperature range (600–1500 °C). An intergranular siliceous impurity (SiO₂) was present in conjunction with the Mg-rich phase. This impurity and the Mg-rich phase acted as a barrier layer for oxygen ion diffusion. The presence of the intergranular phases (i.e. the monoclinic and Mg-rich phases) contributed to the degradation of the ionic conductivity in Mg-PSZ with an Al₂O₃ addition.     

Some regularities of the fracture of ordered alloys based on Ni3Fe

Some regularities of the fracture of ordered polycrystals of the alloys Ni₃Fe, Ni₃(FeMn), Ni₃FeAl), Ni₃(FeCr), Ni₃(FeCr) are studied. The alloys Ni₃Fe, Ni₃(FeMn), and Ni₃(FeAl) possess low plasticity in the ordered state at the test temperatures T < 100 °C. In the 100–200 ° C temperature range a brittleness-viscosity transition is detected which is analogous to that observed in body centered cubic (BCC) metals and alloys. The transition from the brittle into the plastic state is not accompanied by a change in the metallographic picture of slip. The distinguishing peculiarity of the strain at elevated temperatures is the significant displacement of the grains along the boundaries. The temperature band of the transition from the brittle into the plastic state of ordered alloys in the tempered state (tempering from a temperature below the temperature of the order-disorder transformation) is observed at tempering temperatures above 450 °C (tests at room temperature). The results obtained permit the assumption that a reduction in the plasticity in ordering alloys based on Ni₃Fe is caused by segregation of the impurities along the grain boundaries.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 6, pp. 35–41, June, 1971.     

Mechanochemical Route for the Synthesis of Cobalt Ferrite–Silica and Iron–Cobalt Alloy–Silica Nanocomposites

CoFe₂O₄–SiO₂ and Fe–Co alloy–SiO₂ nanocomposites were prepared by high energy ball milling of Si, -Fe₂O₃, Co₃O₄ and SiO₂ mixtures, followed by thermal treatment under appropriate oxidative/reductive conditions. XRD and TEM measurements carried out after 50 h of milling show highly dispersed unidentified reaction products. Further thermal treatment at 900°C in air leads to spherical CoFe₂O₄ nanocrystals (NCs) with a narrow size distribution centered around 2.5 nm, uniformly dispersed in the amorphous SiO₂ matrix. Reduction of this sample in a H₂ flow at 800°C produces a mixture of dispersed metallic cobalt and iron silicate with traces of Fe–Co alloy NCs. Reduction of the as-milled sample, on the contrary, leads almost completely to Fe–Co alloy NCs uniformly dispersed in the SiO₂ matrix and with an average particles size around 11.2 nm.