Characterization of dislocation interactions in olivine using electron tomography

We have investigated by electron tomography, in a transmission electronic microscope, the interactions between dislocations in olivine single crystals and polycrystals deformed in axial compression at T < 1000 °C (T < 0.5T_m). Dislocations are mostly of the [0?0?1] type, except in the polycrystal where [1?0?0] and [0?0?1] dislocations have been activated. A few 〈1?0?1〉 junctions have been found and characterized. Many collinear interactions have been identified either involving direct interactions between crossing dislocations of opposite Burgers vectors or indirect interactions between dislocations gliding in parallel planes and sessile dislocation loops. We suggest that collinear interaction, already identified as the primary source of strain hardening in FCC metals, is the main dislocation interaction mechanism in olivine deformed at temperatures below 1000 °C.     

Ordinary dislocation configurations in high Nb-containing TiAl alloy deformed at high temperatures

Abstract

High Nb-containing TiAl (Nb–TiAl) alloys possess mechanical properties at elevated temperatures superior to conventional TiAl alloys. However, the strengthening mechanisms induced by Nb addition have been discussed controversial for a long time. In the present study, the dislocation structures in a polycrystalline high Nb–TiAl alloy after tensile tests at 700 and 900 °C were investigated by transmission electron microscope (TEM) observation. The results show that abundant double cross slip of ordinary dislocations is activated in the samples deformed at 700 °C. The dislocations are pinned at the jogs and numerous dipoles are observed. Debris can be commonly observed in the vicinity of screw dislocations. Trace analysis shows that the cross-slip plane is (1?1?0)γ at 700 °C but (1?1?1)γ octahedral plane at 900 °C. Three-dimensional (3D) dislocation structures, caused by cross-slip and annihilation of ordinary dislocations, were observed along the screw orientation. The dipoles and debris produced by high-temperature cross slip can be important for the strengthening of high Nb–TiAl alloys.     

On low temperature glide of dissociated 〈1 1 0〉 dislocations in strontium titanate

An elastic interaction model is presented to quantify low temperature plasticity of SrTiO₃ via glide of dissociated 〈1 1 0〉{1 1 0} screw dislocations. Because 〈1 1 0〉 dislocations are dissociated, their glide, controlled by the kink-pair mechanism at T < 1050 K, involves the formation of kink-pairs on partial dislocations, either simultaneously or sequentially. Our model yields results in good quantitative agreement with the observed non-monotonic mechanical behaviour of SrTiO₃. This agreement allows to explain the experimental results in terms of a (progressive) change in 〈1 1 0〉{1 1 0} glide mechanism, from simultaneous nucleation of two kink-pairs along both partials at low stress, towards nucleation of single kink-pairs on individual partials if resolved shear stress exceeds a critical value of 95 MPa. High resolved shear stress allows thus for the activation of extra nucleation mechanisms on dissociated dislocations impossible to occur under the sole action of thermal activation. We suggest that stress condition in conjunction with core dissociation is key to the origin of non-monotonic plastic behaviour of SrTiO₃ at low temperatures.     

High-temperature creep of single-crystal nickel-based superalloy: microstructural changes and effects of thermal cycling

Creep tests were performed on MC2 single crystal superalloy at 950°C/200?MPa and 1150°C/80?MPa under isothermal and thermal cycling conditions with a tensile axis along the [0?0?1] direction. It was found that the thermal cycles strongly affect the creep behavior at 1150°C but not at 950°C. This was related to the repetitive precipitation and dissolution of small γ′ rafts at the higher temperature, as revealed by quantitative characterization of the γ/γ′ microstructure. The dislocation microstructure exhibits similar trends in all the tested conditions, with a very high activity of a[1?0?0]-type dislocations climbing through the rafts. Such climbing dislocations constitute a recovery process for the deformation active system. It appears that the density of a[1?0?0] dislocations, and not their climb velocity or diffusion rate, is the key parameter for the control of creep rate. The thermal cycles, which imply the creation and subsequent dissolution of rafts, provided new dislocations, which explains the acceleration of creep observed under such conditions.     

Effects of Al concentration and resulting long-period superstructures on the plastic properties at room temperature of Al-rich TiAl single crystals

The role of Al₅Ti₃ and h-Al₂Ti long-period superstructures on the plastic properties of TiAl at room temperature is investigated on five single crystals with aluminium content comprised between 54.7 at.%, and 62.5 at.%. After annealing at 1200°C for 1?h, the Al₅Ti₃ superstructure develops in the L1₀ (γ) matrix upon increasing Al concentration except for Ti–62.5 at.%Al where h-Al₂Ti substitutes for Al₅Ti₃. The CRSS for <110]{111} first increases abruptly with the development of the Al₅Ti₃-type ordering. Then, the CRSS reaches a plateau at which dislocations assemble in groups of four to prevent extra anti-phase boundary (APB) from being engendered during glide throughout the Al₅Ti₃ phase. In Ti–62.5 at.%Al, the CRSS for ordinary slip further increases upon the precipitation of h-Al₂Ti in the L1₀ phase, whereas it decreases when the crystal is fully transformed into single-phased Al₅Ti₃. <101] superlattice dislocations are primarily activated under both the [210] and [1?1?8.6] load orientations irrespective of the Al concentration, but the dislocation microstructure strongly depends on orientation as well as on the degree of Al₅Ti₃ ordering. In the [210] orientation, the frequency of the decomposition of <101] dislocations into 1/2<110] and 1/2<112] dislocations decreases abruptly with the development of Al₅Ti₃. This is interpreted in terms of the increased difficulty to move ordinary dislocations. Under the [1?1?8.6] orientation, the density of faulted dipoles diminishes remarkably with the development of Al₅Ti₃. This is consistent with the transformation of the low energy extrinsic stacking fault of the L1₀ phase into a higher energy complex extrinsic stacking fault.     

Local configurations and atomic intermixing in as-quenched and annealed Fe1−xCrx and Fe1−xMox ribbons

Local atomic configuration, phase composition and atomic intermixing in Fe-rich Fe_1?xCr_x and Fe_1?xMo_x ribbons (x = 0.05, 0.10, 0.15), of potential interest for high-temperature applications and nuclear devices, are investigated in this study in relation to specific processing and annealing routes. The Fe-based thin ribbons have been prepared by induction melting, followed by melt spinning and further annealed in He at temperatures up to 1250 °C. The complex structural, compositional and atomic configuration characterisation has been performed by means of X-ray diffraction (XRD), transmission Mössbauer spectroscopy and differential scanning calorimetry (TG-DSC). The XRD analysis indicates the formation of the desired solid solutions with body-centred cubic (bcc) structure in the as-quenched state. The Mössbauer spectroscopy results have been analysed in terms of the two-shell model. The distribution of Cr/Mo atoms in the first two coordination spheres is not homogeneous, especially after annealing, as supported by the short-range order parameters. In addition, high-temperature annealing treatments give rise to oxidation of Fe (to haematite, maghemite and magnetite) at the surface of the ribbons. Fe_1?xCr_x alloys are structurally more stable than the Mo counterpart under annealing at 700 °C. Annealing at 1250 °C in He enhances drastically the Cr clustering around Fe nuclei.     

Mechanisms of high-temperature creep of nickel-based superalloys under low applied stresses

[001] single-crystal specimens of the superalloys CMSX-4 and CMSX-10 were tested for creep at 1100°C under tensile stresses between 105 and 135?MPa, where they show pronounced steady creep. The deformed superalloys were analysed by density measurements, scanning electron microscopy and transmission electron microscopy which supplied information about porosity growth, evolution of the γ–γ′ microstructure, dislocation mobility and reactions during creep deformation. It is shown that, under the testing conditions used, steady creep strain mostly results from transverse glide–climb of (a/2) ?011? interfacial dislocations. A by-product of the interfacial glide–climb are vacancies which diffuse along the interfaces to growing pores or to a ?100? edge dislocations climbing in the γ′ phase. Climb of a ?100? dislocations in the γ′ phase is a recovery mechanism which reduces the constraining of the γ phase by the γ′ phase, thus enabling further glide of (a/2) ?011? dislocations in the matrix. Moreover the γ′ dislocations act as vacancy sinks facilitating interfacial glide–climb. The creep rate increases when the γ–γ′ microstructure becomes topologically inverted; connection of the γ′ rafts results in extensive transverse climb and an increase of the number of a?100? dislocation segments in the γ′ phase.     

Generation of dislocations introduced by bending stress in a Si wafer

Distribution and morphology for dislocations introduced in (001) Si wafers subjected to bending stress at 800°, 900°, and 1100°C were investigated. For wafers bent around a [110] axis at 900° and 1100°C, straight dislocations appeared along the [110] direction only near the neutral plane, and were absent at the surfaces where bending stress is greatest. However, for wafers bent at 800 °C, such straight dislocations were not formed. Dependence of the dislocation distribution and morphology on heat treatment temperature is explained on the basis of interaction between bending stress and SiO₂ precipitates introduced in bulk. Also, it was found that the straight [110] dislocations remained still near the neutral plane, even when additional reverse bending stress was applied around an axis parallel to the dislocations, but were transfered toward the tensile surface by bending around an axis normal to the dislocation direction.     

The activation and the spreading of deformation in a fully lamellar Ti–47 at.% Al–1 at.% Cr–0.2 at.% Si Alloy

The spreading of deformation in a lamellar Ti–47?at.% Al–1?at.% Cr–0.2?at.% Si alloy deformed under compression is studied at 25°C and 600°C. This microstructure is largely dominated by twin-related variants which are separated by either twin interfaces or thin α ₂ slabs. The alloy deforms at both temperatures by ordinary dislocations and twins. Deformation in a particular γ variant and its adjacent twin-related variant involves the same kind of glide system, either ordinary dislocations or twins. This property is found to be true for all twin-related lamellae. The occurrence of this correlated glide is explained by the introduction of the notion of pilot and driven orientations. The lamellar orientation in which the operating glide system is activated on the basis of Schmid factor considerations is termed the pilot orientation. It imposes its deformation system on to the twin-related lamella, called the driven orientation, whose deformation may not involve the slip system most favoured by the applied stress.     

Outside dislocations generated from phosphorus implanted silicon layers

The growth, movement and nature of outside dislocation, which propagate from heavily phosphorus (>10¹⁵ ions/cm²) implanted (111), (100), and (110) silicon layers into unimplanted outside regions by a compressive strain induced during 1100° C wet O₂ annealing, are investigated using transmission electron microscopy and x-ray diffraction topography. Outside dislocations are formed, mainly on (111) planes., by the glide motion of dislocation networks formed in implanted layers during early annealing. This results in dislocations extending into the unimplanted areas to different degrees, in the order of, from the largest to smallest, (111), (110), and (100) wafers. In (110) wafers, the [001] oriented dislocations in the implanted regions rise to the surface at the implant and unimplant boundary. On the other hand, the [110] dislocations penetrate into the unimplanted region. Two sets of orthogonal 〈110〉 oriented dislocations generated in (100) implanted wafers behave in the same manner as the [001] dislocations in (110) wafers. Some sources of the compressive strain related to the generation of these dislocations are discussed.     

Dissociation of non-screw dislocations in B.C.C. lattice

A non-planar dissociation of non-screw 1/2[¯111] (110) dislocations is proposed. The dissociation is possible for dislocations of [1¯11] and [1¯10] directions and the dislocations of these directions become sessile. The [1¯11] and [1¯10] directions are in agreement with experimentally observed shape of dislocations in the (110) glide plane.     

Cellulose-derived carbons as a high performance anodic material for Na-ion battery

A facile and easily scalable method for producing disordered carbons as active materials for sodium ion (Na-ion) battery anode has been developed. The materials were synthesized by two-step pyrolysis of microcrystalline cellulose at the final temperature in the range of 950 to 1250 °C, followed by pyrolytic carbon (PC) coating. The effect of heat-treatment temperature (HTT) and PC process on heteroatom content (elemental analysis), porous texture (N₂ and CO₂ adsorption), and electrochemical performance (coin-type half-cell) was analyzed. Increasing HTT results in remarkable decrease of oxygen content, from 4.4 to 1.4 wt.%, and the surface area accessible for N₂ molecules (microporosity), from 502 to 114 m² g^?1, while the carbonization degree, expressed as the H/C atomic ratio and the area probed by CO₂ (ultramicropores) are only slightly reduced. Elevating carbonization temperature gradually decreases the irreversible C_irr and increases the reversible C_rev capacities in the first charge/discharge cycle. PC coating, applied to 1000 °C, seems to be less effective in improving electrochemical properties than HTT factor despite strong reduction of porosity and surface chemistry. Simple heat treatment at 1200 °C seems to be optimal to produce anodic material with the best electrochemical performance in a wide range of current load: coulombic efficiency of 0.78 and C_rev of 306 or 261 mAh g^?1 at 20 or 500 mA g^?1, respectively.     

The peierls energy and kink energy in fcc metals

In fcc crystals, dislocations are dissociated on the {111} glide plane into pairs of partial dislocations. Since each partial interacts individually with the Peierls potential and is coupled to its neighbour by a stacking fault, periodic variations in the separation distance d of the partials occur when dislocations running along closed packed lattice directions are displaced. This can drastically reduce the effective Peierls stress. By using the Peierls model the structure of 0°, 30°, 60° and 90° dislocations in a typical fcc metal with the elastic properties of Cu and a stacking-fault energy γ₀ in the interval 0.04?≤?γ₀?≤?0.05?J/m² was studied, and the magnitude of the Peierls energy ΔE _P and the resulting kink energies E _K were determined. Since the energies involved are of the order of 10^?3?eV/b or less, their magnitude cannot be asserted with high confidence, considering the simplifying assumptions in the model. The difference in the changes of the core configuration during displacement of dislocations of different orientations should, however, be of physical significance. It is found that a dissociated 60° dislocation generally has a higher effective Peierls energy than a screw dislocation, but the reverse is true for the kink energy, at least in Cu.     

Triethylbutylammonium bis(trifluoromethanesulphonyl)imide ionic liquid as an effective electrolyte additive for Li-ion batteries

Ionic liquids are promising additives for Li-ion batteries owing to its desirable physicochemical properties. Triethylbutylammonium bis(trifluoromethanesulphonyl)imide ([N₂₂₂₄][Tf₂N]) ionic liquid was synthesized and their physical and electrochemical properties were investigated. Among several quaternary ammonium ionic liquids, [N₂₂₂₄][Tf₂N] exhibited higher conductivity (1.31 mS?cm^?1), better thermal and electrochemical stabilities, and wide electrochemical window, i.e., more than 5.9 V. Standard solution was prepared by dissolving lithium bis(trifluoromethanesulphonyl)imide (LiTf₂N) in ethylene carbonates/dimethyl carbonate (1:1, by weight). The conductivity for the electrolyte containing [N₂₂₂₄][Tf₂N] and the mixed electrolyte without additives at 25 °C are 10.24 and 8.79 mS?cm^?1, respectively. LiFePO₄ half-cell containing 0.6 mol?L^?1 LiTf₂N-based organic electrolyte with [N₂₂₂₄][Tf₂N] showed relatively high initial discharge capacity and coulombic efficiency at first cycle. It is found that the mix [N₂₂₂₄][Tf₂N] electrolyte exhibits relatively high-rate capacity. The capacity retention of half-cell containing [N₂₂₂₄][Tf₂N] is 2 % more than without additive at 0.2 C. However, the rate capacity retention of the half-cell with mix [N₂₂₂₄][Tf₂N] electrolyte is above 10 % more than without additive at 0.5 C. The results showed that [N₂₂₂₄][Tf₂N] was an effective electrolyte additive in LiFePO₄ half-cell.     

Genesis,structural, and transport properties of La<Subscript>2</Subscript>Mo<Subscript>2-x</Subscript>W<Subscript>x</Subscript>O<Subscript>9</Subscript> prepared via mechanochemical activation

Fast oxide-ion conductors La₂Mo_2-xW_xO₉ (x = 0–1) have been prepared using mechanochemical activation (MA) of starting oxides in a high-power planetary ball mill. Studies of La₂Mo_2-xW_xO₉ genesis and structural properties using thermal analysis, XRD, SEM, IR, and Raman spectroscopy have revealed that MA results in the formation of an amorphous precursor, while the cubic β-phase is formed after calcination at 700–900 °C. Due to a high dispersion of powders, high-density pellets of W-LAMOX ceramics have been obtained already after sintering at 950 °C. Their electrical conductivity measured by the impedance spectroscopy depends on the W concentration being sufficiently high (up to 5.6?10^?3 S/cm at 630 °C) at temperatures below 650 °C.     

Monazite (monoclinic LaPO4) slip systems at room temperature

Polycrystalline monazite (monoclinic LaPO₄) was deformed by spherical indentation at room temperature. Slip systems were identified using TEM of thin sections prepared parallel and close to the indented surface. Dislocation Burgers vectors (b) were identified by Burgers circuit closure in high resolution TEM images, supplemented by diffraction contrast where possible. A total of 441 b determinations were made in 97 grains. The most common slip systems were [001]/(010), [100]/(010) and [010]/(100). Slip on (001) was less common. Many other less common slip systems and Burgers vectors were also identified, including b = [101], [101], [011], [110] and [111]. b = [101] dislocations dissociate into ½[101] partials, and b = [101] dislocations are inferred to dissociate to ½[101] partials, with a low energy stacking fault of ～30 mJ/m². b = [100] dislocations may dissociate into ¼[210] + ¼[210] partials. b = [010] may sometimes dissociate to ½[010] + ½[010] partials. Other types of partial dislocations were also observed and discussed. All partial dislocations were climb dissociated. The line energies of monazite dislocations and their partials were calculated, and stacking fault structures for partial dislocations are analyzed. Satisfaction of the Von Mises criterion for full ductility most likely involves [101]/(111) and ?011?/{011} or {111} slip, but other combinations that require both b = [101] and ?011? or ?110? are possible. If deformation twinning is active, slip systems with b = ?011? or ?110? may not be necessary for full ductility.     

The Fe–Fe2P phase diagram at 6 GPa

Here, we report experimental results on melting and subsolidus phase relations in the Fe–Fe₂P system at 6?GPa and 900–1600°C. The system has two P-bearing compounds: Fe₃P and Fe₂P. X-ray diffraction patterns of these compounds correspond to schreibersite and barringerite, respectively. The Fe–Fe₃P eutectic appears at 1075°C and 16?mol% P. Schreibersite (Fe₃P) melts incongruently at 1250°C to produce barringerite (Fe₂P) and liquid containing 23?mol% P. Barringerite (Fe₂P) melts congruently at 1575°C. Maximum solid solution of P in metallic iron at 6?GPa is 5?mol%. As temperature increases to 1600°C, the P solubility in the metallic iron decreases to 0.5?mol%, whereas the P content in coexisting liquid decreases to 3?mol%. The composition of quenched phases from Fe–P melt coincides with the compositions of equilibrium phases at corresponding temperature. Consequently, the composition of quenched products of Fe-P melts in meteorites can be used for reconstruction of P–T conditions of their crystallization under ambient or low pressures or during shock melting by impact collisions.     

Thermal and electrochemical properties of poly(butylene sulfite)-based polymer electrolyte

Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO₂CF₃)₂, LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO₂F)₂, LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36?×?10^?4 S/cm at 80 °C and 1.01?×?10^?5 S/cm at 20 °C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25?×?10^?3 S/cm at 80 °C and 5.93?×?10^?5 S/cm at 20 °C. Glass transition temperature (T _g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T _g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.     

Bergauf-Diffusion des Phosphors im Silizium

Uphill-Diffusion of Phosphorus in Silicon The drive-in-diffusion of phosphorus in silicon (at 1523 K (1250°C) under pure 0_2? ambient) starting from a prediffused zone shows, investigated by neutron activation analysis, two particulartities:

• 1 Uphill-diffusion of phosphorus in the interior of the silicon crystal takes place near to the Si0_2? Siinterface.
• 2 The total amount of phosphorus contained in the diffusion zone of the silicon crystal in independent from the duration of drive-in-diffusion. There is not any outdiffusion of phosphorus from the silicon crystal into the Si0_2? layer.

It is assumed, that the mentioned uphill-diffusion is caused by an inhomogeneous distribution of point defects (e. g. vacancies), which generates a nonfickian dopant flux component. This means, that Einstein's assumption of a symmetrical propability function for jumps of dopant atoms [21] is not valid in this special case of solid diffusion.     

Highly enhanced low-temperature performances of LiFePO<Subscript>4</Subscript>/C cathode materials prepared by polyol route for lithium-ion batteries

Although LiFePO₄/C has been successfully put into practical use in lithium-ion batteries equipped on new energy vehicles, its unsatisfactory low temperature results in poor low performance of lithium-ion batteries, leading to a much smaller continue voyage course at extreme environments with low temperature for electric vehicles. In this paper, the electrochemical performance of the LiFePO₄/C prepared by polyol route was investigated at a temperature range from 25 to ?20 °C. Compared to commercial ones, as-prepared LiFePO₄/C shows a much better low-temperature performance with a reversible capacity of 30 mA h g^?1 even at 5 C under ?20 °C and a capacity retention of 91.1 % after 100 cycles at 0.1 C under 0 °C. Moreover, high-resolution transmission electron microscopy (HRTEM) revealed that this outstanding performance at low temperatures could be assigned to uniform carbon coating and the nano-sized particles with a highly crystalline structure.