Phase decomposition of liquid-quenched β-type Ti-Cr alloys

Phase decomposition behaviour of liquid-quenched (bcc) type Ti-Cr alloys was investigated by means of transmission electron microscopy and hardness measurements. It was found that decomposition of to ₁ (Ti-rich, bcc) + ₂ (Ti-lean, bcc) takes place in the intermediate composition range of the Ti-Cr system. This experimental result proves the theoretical prediction made by Menon and Aaronson, but the observed ₁ + ₂ two-phase field expands towards higher temperatures than the predicted binodal line. The coherent ₁ + ₂ two-phase state exhibits the so-called 100 modulated structure and it was concluded that the formation of such a structure is a result of spinodal decomposition of the -phase. We obtained time-temperature-transformation (TTT) diagrams of -type Ti-30, 40 and 50 at % Cr alloys. A typical sequence of structural change is coherent ₁ + ₂ incoherent ₁ + ₂ incoherent ₁ + ₂ + grain boundary precipitates stable state of + TiCr₂ or + TiCr₂. Not all the states in the above sequence appear, depending on alloy composition, liquid-quenching rate and ageing temperature.     

Solid state phase transformation of BaB2O4 during the isothermal annealing process

Solid-state phase transformation of BaB₂O₄ during the isothermal annealing process for both to and to were investigated using a platinum crucible. For the -phase crystal at the -phase stable temperature (> 925 °C), the phase transforms to the phase perfectly below the melting temperature of 1100 °C. Meanwhile, for the -phase crystal at the -phase stable temperature (< 925 °C), the phase transforms to the phase perfectly above 800 °C. There is some difference in phase transformation behaviour between bulk-shape crystals and the powder, caused by thermal stress.     

Mechanical properties and microstructure of β-SiAION-β-SiC composites by pressureless sintering

-SiAION--SiC composites containing up to 12 wt% -SiC were prepared by pressureless sintering. The strength of composites at room temperature remained relatively unchanged, whereas strength at 1200 °C increased for composites. The fracture toughness (K _IC) for composites was higher than that for -SiAION ceramics. The maximum value was 5.4 MPa m^1/2 for 6 wt% -SiC, and this was an improvement of 15% in comparison with -SiAION ceramics. From SEM observations, an improvement inK _IC values was attributed to crack deflections and branching-off of cracks. Intra-granular fractures were frequently observed in -SiAION. From TEM observations, -SiAION crystals were nanocomposites, within which existed the fine crystals in -SiAION crystal. For composite, -SiAION and -SiC crystals were directly in contact. The mismatching zone was observed in -SiC.     

EPMA mapping of small particles of α-AlFeSi and β-AlFeSi in AA6063 alloy billets

It is well known that the spatial distribution and the spatial density of the particles o-AlFeSi and -AlFeSi in the billets of Al-Mg-Si alloys, such as AA6063 alloys affect the quality of anodizing performance of their extrusions. For this reason it is very important to control the spatial distribution and the spatial density of both AlFeSi particles at extrusion plants. The X-ray diffraction method (XRD) has been used for discrimination between -AlFeSi and -ALFeSi particles. However it is not an appropriate method for determining the spatial distributions of particles in the alloys. As an alternative method an electron probe microanalyzer (EPMA) has been used for determining the spatial distributions of each element in the microstructures. However, unfortunately it is difficult to discriminate between the particles composed of the same elements like -AlFeSi and -AlFeSi particles. Thus, we tried to develop a convenient method to discriminate between -AlFeSi and -AlFeSi particles in the microstructure of AA6063 alloys and developed the EPMA mapping of -AlFeSi and -AlFeSi particles. First, in order to discriminate between the two particles, we tried to use the relative X-ray intensity ratio, the I _Fe/I _Si ratio instead of the Fe/Si mass ratio. Then, we calculated the value of the I _Fe/I _Si ratio from -AlFeSi and -AlFeSi by using Monte Carlo calculations and obtained the critical value of the I _Fe/I _Si ratio, to distinguish between -AlFeSi and -AlFeSi. After that, using the discrimination value, we developed the EPMA mapping program (EPMA method) to observe the distributions of -AlFeSi and -AlFeSi, and to calculate the areas (%) of -AlFeSi and -AlFeSi. Finally, we checked the correlation between the EPMA and the XRD methods. Consequently, the two methods were in good agreement. Today, this EPMA method instead of the XRD method is successfully used in the quality control of 6063 aluminum alloy billets after heat treatment at our aluminum extrusion works.     

Variation of aluminium concentration in β′-sialon grains formed during liquid-phase sintering of Si3N4-Al2O3-Nd2O3

The aluminium concentration in -sialon grains of the 74Si₃N₄ ()-6Al₂O₃-20Nd₂O₃ (wt%) specimen has been determined. As the - transformation proceeded, the average aluminium concentration in -sialon grains decreased. For individual grains, the aluminium concentration at the centre was higher than that at the edge. The observed variation of aluminium concentration has been explained in terms of the compositional change of the liquid matrix during sintering.     

Precipitation of β particles in a fully lamellar Ti-47Al-2Nb-1Mn-0.5W-0.5Mo-0.2Si (at.%) alloy

The precipitation of (B2) particles at intermediate temperatures, between 760°C and 1050°C, is investigated in a fully lamellar TiAl-WMoSi alloy. The particles, having a thin-plate shape, usually precipitate on the ₂ side of ₂/ interfaces at low aging temperatures in an uneven two-dimensional growth mode. While those formed at higher aging temperatures, growing extensively within the ₂ plate and into the adjacent lamellae, have an ellipsoid shape. The growth of particles at low aging temperatures yields an activation energy of about 366 kJ/mol. It is suggested that at low aging temperatures the growth of particles proceeds via an ₂ precipitation process controlled by diffusion of W and Mo along the /₂ and / interfaces.     

Elevated temperature deformation behaviour of multi-phase Ni-20 at % Al-30 at % Fe and its constituent phases

The mechanical behaviour of the multi-phase ( + /) alloy Ni-20 at % Al-30 at % Fe and alloys similar to its constituent and / phases, Ni-30 at % Al-20 at % Fe and Ni-12 at % Al-40 at % Fe, respectively, were investigated. When tested in tension at 300 K, the alloys exhibited 20%, 2% and 28% elongation, respectively. At elevated test temperatures (700, 900 and 1100 K), the multi-phase alloy exhibited increased ductility, reaching an elongation in excess of 70% at 1100 K without necking or fracture. Similarly, the alloy demonstrated increased ductility with increasing test temperatures. In contrast, the / alloy showed greatly reduced ductility with increasing temperature and was quite brittle both at 900 and 1100 K. Thus, whilst at room temperature the / phase improved the ductility of the + / aggregate, at elevated temperatures the phase alleviated the brittleness of the / phase, thereby preventing any embrittlement of the multi-phase alloy over the temperature range 300–1100 K. Also, whilst the phase improved the room-temperature strength of the multi-phase alloy, at elevated temperatures where the phase is known to be weak, the / phase improved the strength of the multi-phase alloy up to 900 K, beyond which the strength deteriorated due to disordering and lack of anomalous strengthening in the / component.     

Structure of martensite formed in Cu-Al-Fe single crystals duringin situ HVEM pseudoelastic tensile experiment

Single crystals of the CuAlFe alloy, containing 14.5 wt% Al and 2.2 wt% Fe were subjected toin situ tensile experiment using straining attachment in a 1 MV electron microscope. Loadelongation curves were obtained for three foil plane/tensile direction orientations: (001) [0 1 0], (0 0 1) [1 1 0] and (1 1 0) [¯1 1 2]. Each crystal was subjected to two cycles of pseudoelastic deformation up to maximum 2% strain, showing almost complete shape recovery. Structure observations and electron diffraction pattern indicated that during deformation of samples of (0 0 1) [1 1 0] and (1 1 0) [1 1 2] orientations, formation of ₁ martensite was observed and only at later stages narrow needles of ₁ nucleate in front of ₁. During pseudoelastic deformation in the (0 0 1) [1 0 0] direction, martensite forms as a mixture of narrow plates possessing either 2H or 18R structures. The following crystallographic relationship between the parent phase and both types of martensite was observed: [1 00] ₁ [101] ₁ and (0 0 1) ₁ (0 1 0)₁;(0 0 1) ₁ (0 1 0) ₁ and [1 1 0] ₁ [0 0 1] ₁. From the character of sidebands reflections presence of 1 0 1 1 0¯1 static displacement waves was inferred.     

Analysis of Rheological Equations Involving More Than One Fractional Parameters by the Use of the Simplest Mechanical Systems Based on These Equations

The behaviour of rheological models containing more than onefractional derivative or fractional operator of fractional orders areinvestigated. All rheological models discussed can be separated intothree groups depending on magnitudes of the value_*/_* (where_* and _* are the orders ofsenior fractional derivatives of stress and strain, respectively): themodels are thermodynamically admissible only when_*/_* = 1 (the first group),thermodynamically compatible only for_*/_* 1 (the secondgroup) and, finally, thermodynamically well-conditioned both at_*/_* 1 and_*/_* > 1 (the third group).It is shown that, under nonstationary excitations, thebehaviour of the simplest mechanical systems (mechanical oscillators,finite and semi-infinite viscoelastic rods), based on the consideredrheological models, may be different (from the point of view ofthermodynamics) from that of the underlying rheological models. Thus,under impulse excitations, the mechanical models based on rheologicalmodels of the first and second groups become thermodynamicallyadmissible not only at_*/_* = 1 but alsowhen _*/_* < 1(mechanical models of group I), but mechanical models based onrheological models of the third group remain thermodynamicallywell-conditioned at the same magnitudes of rheological parameters as thecorresponding rheological models do (mechanical models of group II). Asthis takes place, group I mechanical models possess diffusion-wavefeatures, that is at_*/_*=1 the stress waves ina semi-infinite rod propagate at a finite speed, and the roots ofcharacteristic equations (for nonstationary vibrations of a mechanicaloscillator or a rod of finite length) as functions of the relaxation orretardation times, behave in a way similar to the characteristicequation roots of rheological models possessing instantaneous elasticity(models of the Maxwell type). When_*/_*<1, the stress wavesin a semi-infinite rod propagate instantaneously at infinitely largespeeds, and the roots of characteristic equations (under nonstationaryvibrations of a mechanical oscillator or a rod of finite length) asfunctions of relaxation times behave in a way similar to thecharacteristic equation roots of rheological models lackinginstantaneous elasticity (models of the Kelvin–Voigt type).Mechanical models from group II possess pure wave or pure diffusionfeatures at all magnitudes of_*/_*.     

Interface characterization of a β-SiC whisker-Al composite

The nature of the interface, the orientation relationship of -SiC whisker (-SiC_w)-Al combination, and the misfit dislocation structures at the -SiC_w-Al interfaces in a -SiC_w-Al composite have been observed by a high-resolution transmission electron microscopy (HRTEM). It was shown that quite a good bonding between the whisker and the aluminium was achieved due largely to the lattice match between SiC and aluminium at the interfaces. The orientation relationship between the whisker and the aluminium was {002}_SiC{111}_Al; 110_SiC110_Al. The interface was clean, faceted and semicoherent. The misfit dislocation cores were located in the whisker side away from the -SiC_w-Al interfaces.     

Bone formation induced by calcium phosphate ceramics in soft tissue of dogs: a comparative study between porous α-TCP and β-TCP

Two kinds of tri-calcium phosphate ceramics (Ca/P = 1.50), -TCP and -TCP, which has the same macrostructure and microstructure, but different phase composition, were implanted in dorsal muscles of dogs. The samples were retrieved at 30, 45 and 150 days, respectively, after implantation, and were analyzed histologically. There were critically different tissue responses between -TCP ceramic and -TCP ceramic. Higher cell populations were observed inside the pores of -TCP than those of -TCP, bone tissue was found in -TCP at 45 and 150 days, but no bone formation could be detected in any -TCP implants in this study. On the other hand, the bone tissue in -TCP seemed to degenerate at 150 days. The results indicate that porous -TCP can induce bone formation in soft tissues of dogs; while the rapid dissolution of the ceramic and the higher local Ca²⁺, PO ₄ ^3- concentration due to the rapid dissolution of -TCP may resist bone formation in -TCP and the less rapid dissolution of -TCP may be detrimental to already formed bone in -TCP.     

Investigation of Phase Evolution During the Thermochemical Synthesis of Tricalcium Phosphate

The formation of tricalcium phosphate (TCP) from dicalcium phosphate and calcium carbonate was investigated using differential thermal analysis (DTA), thermogravimetric analysis (TGA), and powder X-ray diffraction (XRD). DTA showed three distinct thermal events attributed to dehydration of dicalcium phosphate dihydrate (brushite, DCPD) to dicalcium phosphate anhydrous (monetite, DCPA), the formation of beta-calcium pyrophosphate (-Ca₂P₂O₇), and the calcination of calcium carbonate. TGA showed three weight losses corresponding to the three thermal events, respectively. XRD analysis showed that -TCP formed, beginning at about 900°C, by the reaction of -Ca₂P₂O₇ with CaO and -TCP changed to -TCP above 1200°C. Further examination of the formation of TCP from calcium hydroxide (Ca(OH)₂) and DCPA showed that -TCP would form only after the decomposition of Ca(OH)₂ to CaO and from the reaction of CaO with -Ca₂P₂O₇ at a fairly low temperature of 800°C. In addition, by naturally cooling -TCP, formed at 1300°C within the heating furnace, to room temperature, it was difficult to obtain a pure phase of -TCP. The proposed mechanism of the reaction to form TCP may include the dehydration of brushite to monetite, dehydration of monetite to beta-calcium pyrophosphate, decomposition of calcium carbonate, the formation of -TCP, and phase transition.     

The redistribution of alloying elements by rapid-heating solution treatment of an (α +β) titanium alloy

Thin-foil X-ray energy-dispersive chemical analysis of an (+) titanium alloy has been used to establish the compositional profiles which develop between the and phases as a result of heating into the field at a rate of 100 K sec^–1. The results show that phase transforms to via a diffusional mechanism as it is progressively enriched in-stabilizing solutes. Complete diffusional transformation of to occurs 160 K above the transus but the phase remains chemically inhomogeneous. On subsequent quenching at a rate of 400 K sec^–1, phase containing less than approximately 10wt% Mo equivalent of -stabilizing solutes transforms to martensite. The proposed transformation mechanisms are consistent with the results of resistivity measurements made during the heating and cooling cycles.     

TEM study of metastable β-phase decomposition in rapidly solidified Ti-6Al-4V alloy

A new rationale is presented for various decomposition products obtained from the metastable -phase found in Ti-6A1-4V alloy produced by hot isostatic pressing comminuted melt-spun fibres and cooled to room temperature by furnace cooling. This alloy has an -matrix with about 8 vol% retained -phase, which is supersaturated with -stabilizers to such an extent that the martensitic transformation has been suppressed. The metastable -phase decomposes by different modes during continuous cooling, depending on the actual composition of individual -grains. Less enrichment of vanadium and iron favours the direct formation of the equilibrium -phase from the -matrix, while greater enrichment of vanadium and iron leads to a spinodal decomposition of the metastable -phase, resulting in a + two-phase structure. During further continuous cooling, the -phase which is lean in -stabilizers will transform into isothermal -phase. In addition, an unknown phase has also been observed in the -phase, which is typified by the appearance of 1/2{112} reflections in the SAD patterns.     

Crystallization of some spodumene-lithium zinc orthosilicate glasses

By using thermal analysis, X-ray diffraction, polarizing and electron microscopy the effect of compositional variation, thermal treatment and nucleation catalysts TiO₂ and ZrO₂ on the nature, type and stability fields of the crystallizing phases, as well as the resulting microstructures, is described for some stoichiometric glass compositions within the system LiAlSi₂O₆-Li₂ZnSiO₄. Intense uniform volume crystallization was achieved. Transparent glass-ceramics with ultrafine microstructures could also be obtained at temperatures near 700 °C. Crystallization begins with the formation of a proto - and/or _II-Li₂ZnSiO₄ followed by, or concomitant with, -eucryptite ss. The proto -phase was formed over a narrow temperature range and rapidly transformed into its _II-modification which, although showing a wider stability range, ultimately transformed into the stable _o-modification. The metastable -eucryptite ss starts its transformation into -spodumene around 800 °C. By prolonged heating at temperatures as high as 1000–1040 °C, -spodumene and _o-Li₂ZnSiO₄ were the main stable end products. TiO₂ and ZrO₂ have contrasting effects on the stability of the LiZn orthosilicates and -eucryptite ss -spodumene transformations. The former exhibits a catalytic effect and the latter showed a retarding effect on these processes.     

Distribution of α-AlFeSi and β-AlFeSi particles in surface layer of AA6063 alloy billets after heat treatment

We developed the EPMA mapping method of small -AlFeSi(Al_8.3Fe₂Si) and -AlFeSi(Al_8.9Fe₂Si₂) particles in the billets of Al-Mg-Si alloys such as AA6063 alloys. To discriminate between -AlFeSi and -AlFeSi particles we used the relative X-ray intensities of Fe/Si ratio, the I _Fe/I _Si ratio, instead of the Fe/Si mass ratio. To obtain the I _Fe/I _Si ratio, we used a Monte Carlo method. In this study, using this method the mapping of -AlFeSi and -AlFeSi particles in the surface layer of AA6063 billets after the heat treatment (for 2 h at 580°C) was done. Namely, the distribution of -AlFeSi and -AlFeSi particles of zones from the billet surface to a depth of 800 m was measured. Results showed the zone from the surface to a depth of 200 m was occupied mainly by -AlFeSi particles and the zone from a depth of 200 m toward the center was occupied mainly by -AlFeSi particles. From these results, it was found that if we remove zones from the surface to a depth of 200 m, we can remove the majority of the -AlFeSi particles, and thus improve the quality of anodizing performance of Al-Mg-Si alloys extrusions.     

Precipitation of chromium containing phases in aluminide coated nickel-base superalloy single crystals

The precipitation of chromium-containing phases, in both the B2 type -phase coating matrix (nominally NiAl) and the substrate of high-activity-pack-aluminized single crystals of a nickel-base superalloy, is considered in this paper. An edge-on transmission electron microscopy (TEM) technique is employed to examine the precipitation of M₂₃X₆, , -Cr and other phases after coating and diffusion treatment and subsequent post-coating treatment at 850 and 950 °C. Initial precipitation is dominated by the formation of M₂₃X₆ in both the coating and substrate, however, in the case of single-crystal substrates the formation of this carbon-rich phase is not sustained. M₂₃X₆ precipitation is superceded by the formation of coherent precipitates of the -Cr phase which effectively retains the basis but removes the superlattice of the -matrix. Extensive precipitation of -Cr has the effect of changing the balance of chromium to molybdenum in solution in the -phase and further precipitation is dominated by -phase intermetallics and other Cr-Mo-containing phases.     

Synthesis of acicular iron oxide nanoparticles and their dispersion in a polymer matrix

An alternative forced hydrolysis approach for the synthesis of -FeOOH of varying dimensions was achieved. The -FeOOH particles were converted into -Fe₂O₃ in a colloidal process, which eliminated the agglomeration of -Fe₂O₃ particles. The acicular -Fe₂O₃ nanoparticles could be readily dispersed into an organic solvent. Preliminary studies have demonstrated that the dispersion of the -Fe₂O₃ nanorods in a polymer matrix is feasible leading to an organic-inorganic nanocomposite.     

Structural transformation during sintering and annealing of beta alumina

Changes in the phase content, microstructure and lattice parameter are observed in stabilized/ alumina specimens following extended sintering and annealing treatments. The resulting state is dependent on composition of the starting powder and on temperature and duration of heat treatment; the kinetics of transformation between and alumina are generally slow and certain/ ceramics remain in a metastable state even after a prolonged high temperature anneal. Following post-sinter heat treatment, splitting of X-ray diffraction peaks reveals a segregation of the phase into two components of differing lattice parameter. With sintering schedules of a long duration the splitting may even be present in the as-fired condition as recently reported by Harbach [1]. The splitting is attributed to a structural change resulting from the expulsion of Na₂O from supersaturated grains.     

Effects of temperature and magnetization on the maximum solubility of 3He in 4He

The laws x^m=x^m(T=0)(1+ _T T²) and x^m=x^m(B=0)(1+ _M B²), giving the effects of temperature and magnetization on the maximum solubility of ³He in ⁴He, are derived using the theory of normal Fermi systems. The parameters _T and _M are expressed in terms of measurable quantities, such as the specific heat and the magnetic susceptibility of the pure and dilute phases. Our relations are consistent with the experimental measurements of _T at SVP and predict a significant dependence of _T on pressure. Estimates of the parameter _M are given. The effects of temperature and magnetization on the osmotic pressure are also discussed.INFN sezione di Padova, gruppo collegato di Trento.