Symmetry-breaking transitions in equilibrium shapes of coherent precipitates: Effect of elastic anisotropy and inhomogeneity

We examine the symmetry-breaking transitions in equilibrium shapes of coherent precipitates in two-dimensional (2-D) systems under a plane-strain condition with the principal misfit strain components epsilon(xx)*. and epsilon(yy)*. For systems with cubic elastic moduli, we first show all the shape transitions associated with different values of t = epsilon(yy)*/epsilon(xx)*. We also characterize each of these transitions, by studying its dependence on elastic anisotropy and inhomogeneity. For systems with dilatational misfit (t = 1) and those with pure shear misfit (t = -1), the transition is from an equiaxed shape to an elongated shape, resulting in a break in rotational symmetry. For systems with nondilatational misfit (-1 < t < 1; t not equal 0), the transition involves a break in mirror symmetries normal to the x- and y-axes. The transition is continuous in all cases, except when 0 < t < 1. For systems which allow an invariant line (-1 less than or equal to t < 0), the critical size increases with an increase in the particle stiffness. However, for systems which do not allow an invariant line (0 < t less than or equal to 1), the critical size first decreases, reaches a minimum, and then starts increasing with increasing particle stiffness; moreover, the transition is also forbidden when the particle stiffness is greater than a critical value.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen

Cathodic reduction of oxygen in fuel cells is known to be enhanced on platinum alloys in relation to the platinum metal. The higher performance of the platinum alloys is as a result of the improved oxygen-reduction kinetics on the alloys but there is hardly any increase in the electrode platinum-surface-areas for the platinum alloys as compared to the platinum metal, and thus the higher performance is solely due to the enhanced electrocatalytic activity of the alloys as compared to the platinum metal. The present X-ray photoelectron spectroscopic (XPS) study on carbon-supported Pt, Pt–Co and Pt–Co–Cr electrocatalysts suggests the presence of a relatively lower Pt-oxide content on the alloys. The X-ray powder diffraction patterns for these electrocatalysts show that while the carbon-supported platinum electrocatalyst has a face-centered cubic (fcc) phase, carbon-supported Pt–Co and Pt–Co–Cr electrocatalysts exhibit a face-centered tetragonal (fct) phase. But, Pt electrocatalyst has a lower particle-size and, hence, a higher dispersion. Previous studies have shown higher activities on the Pt-alloys than on Pt, and have attributed it to changes in the electronic and structural characteristics of Pt. These changes can be correlated with the lower oxidation-state of Pt sites, as found in this study.

Low temperature synthesis of ferromagnetic (LaK)MnO3 from KCl, KBr and KI fluxes

Potassium doped lanthanum manganites have been synthesized from KCl, KBr and KI fluxes at 900, 850 and 750 °C respectively. While all the flux-grown oxides are ferromagnetic metals (Tc=290–330 K), the oxides grown from KCl and KBr fluxes crystallize in the rhombohedral structure and that synthesized from KI flux adopts the cubic structure. The enhancement in Tc correlates with the increasing tendency of the flux to get oxidized and decreasing melting points of the flux. Nearly stoichiometric (LaK)MnO3 with 33 % of Mn4+ concentration could be prepared at temperature as low as 750 °C. Composition of all the phases have been obtained from the chemical analysis of the elements present.

Manipulation of the Hydration Levels in Minerals of Sodium Cadmium Bisulfate toward the Design of Functional Materials

Several variants of hydrated sodium cadmium bisulfate, Na(2)Cd(2)(SO(4))(3) center dot 3H(2)O, Na(2)Cd(SO(4))(2) center dot 2H(2)O, and Na(2)Cd(SO(4))(2) center dot 4H(2)O have been synthesized, and their thermal properties followed by phase transitions have been invesigated. The formation of these phases depends on the stochiometry and the time taken for crystallization from water. Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O, which crystallizes in the trigonal system, space group P3c, is grown from the aqueous solution in about four weeks. The krohnkite type mineral Na(2)Cd(SO(4))(2) center dot 2H(2)O and the mineral astrakhanite, also known as blodite, Na(2)Cd (SO(4))(2)center dot 4H(2)O, crystallize concomittantly in about 24 weeks. Both these minerals belong to the monoclinic system(space group P2(1)/c). Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O loses water completely when heated to 250 degrees C and transforms to a dehydrated phase (cubic system, space group I (4) over bar 3d) whose structure has been established using ab initio powder diffration techniques. Na(2)Cd(SO(4))(2)center dot 2H(2)O transforms to alpha-Na(2)Cd(SO(4))(2) (space group C2/c) on heating to 150 degrees C which is a known high ionic conductor and remains intact over prolonged periods of exposure to moisture (over six months). However, when alpha-Na(2)Cd(SO(4))(2) is heated to 570 degrees C followed by sudden quenching in liquid nitrogen beta-Na(2)Cd(SO(4))(2) (P2(1)/c) is formed. beta-Na(2)Cd(SO(4))(2) takes up water from the atmosphere and gets converted completely to the krohnkite type mineral in about four weeks. Further, beta-Na(2)Cd(SO(4))(2) has a conductivity behavior comparable to the a-form up to 280 degrees C, the temperature required for the transformation of the beta- to alpha-form. These experiments demonstrate the possibility of utilizing the abundantly available mineral sources as precursors to design materials with special properties.

Variable temperature x-ray crystal structure analysis of a type I langbeinite: Rb2Cd2(SO4)(3)

The structure of a type I langbeinite, Rb2Cd2(SO4)(3), displays three different phases, cubic with a = 10.378(5) Angstrom (space group P2(1)3) at room temperature, monoclinic at 120 K with a = 10.328(3), b = 10.322(3), c = 10.325(3) Angstrom, beta = 89.975(1)degrees (space group P2(1)), and orthorhombic at 85 K with a = 10.319(2), b = 10.321(2), c = 10.320(2) Angstrom (space group P2(1)2(1)2(1)), respectively. Precise single-crystal analyses of these phases indicate that Rb2Cd2(SO4)(3) distorts initially from cubic to monoclinic upon cooling followed by a significant reorientation of the SO4 tetrahedra, resulting in an orthorhombic symmetry upon further cooling. The three structures have been established unequivocally using the same crystal. There is no indication of the formation of an intermediate triclinic phase or any lattice disorder as conjectured in several earlier reports on compounds belonging to the type I langbeinite. The bond valence sum analyses of the coordination around the Rb sites indicate asymmetry in the bond strengths which could be the driving force of the ferroelectric behavior in these materials.

Microstructural evolution in laser-ablation-deposited Fe–25 at.% Ge thin film

Films with Fe–25 at.% Ge composition are deposited by the process of laser ablation on single crystal NaCl and Cu substrates at room temperature. Both the vapor and liquid droplets generated in this process are quenched on the substrate. The microstructures of the embedded droplets show size as well as composition dependence. The hierarchy of phase evolution from amorphous to body-centered cubic (bcc) to DO3 has been observed as a function of size. Some of the medium-sized droplets also show direct formation of ordered DO19 phase from the starting liquid. The evolution of disordered bcc structure in some of the droplets indicates disorder trapping during liquid to solid transformation. The microstructural evolution is analyzed on the basis of heat transfer mechanisms and continuous growth model in the solidifying droplets.

Evolution of metastable phases during crystallization of pulsed laser deposited amorphous Al–Fe films

Amorphous thin films of different Al–Fe compositions were produced by plasma/vapor quenching during pulsed laser deposition. The chosen compositions Al72Fe28, Al40Fe60, and Al18Fe82 correspond to Al5Fe2 and B2-ordered AlFe intermetallic compounds and α–Fe solid solution, respectively. The films contained fine clusters that increased with iron content. The sequences of phase evolution observed in the heating stage transmission electron microscopy studies of the pulsed laser ablation deposited films of Al72Fe28, Al40Fe60, and Al18Fe82 compositions showed evidence of composition partitioning during crystallization for films of all three compositions. This composition partitioning, in turn, resulted in the evolution of phases of compositions richer in Fe, as well as richer in Al, compared to the overall film composition in each case. The evidence of Fe-rich phases was the B2 phase in Al72Fe28 film, the L12- and DO3-ordered phases in Al40Fe60 film, and the hexagonal ε–Fe in the case of the Al18Fe82 film. On the other hand, the Al-rich phases were Al13Fe4 for both Al72Fe28 and Al40Fe60 films and DO3 and Al5Fe2 phases in the case of Al18Fe82 film. We believe that this tendency of composition partitioning during crystallization from amorphous phase is a consequence of the tendency of clustering of the Fe atoms in the amorphous phase during nucleation. The body-centered cubic phase has a nucleation advantage over other metastable phases for all three compositions. The amorphization of Al18Fe82 composition and the evolution of L12 and ε–Fe phases in the Al–Fe system were new observations of this work.

Effect of Nature of the Precursor on Crystallinity and Microstructure of MOCVD-Grown ZrO2 Thin Films

In the present work, we report the deposition of zirconia thin films on Si(100) at various substrate temperatures by low-pressure metalorganic chemical vapor deposition (MOCVD). Three different zirconium complexes, viz., tetrakis(2,4-pentadionato)zirconium(IV), [Zr(pd)4], tetrakis(2,2,6,6-tetramethyl-3,5-heptadionato)zirconium(IV), [Zr(thd)4], and tetrakis(t-butyl-3-oxo-butanoato)zirconium(IV), [Zr(tbob)4] are used as precursors. The relationship between the molecular structures of the precursors and their thermal properties, as examined by TG/DTA is presented. The films deposited using these precursors have distinctly different morphology, though all of them are of the cubic phase. The films grown from Zr(thd)4 are well crystallized, showing faceted growth at 575°C, whereas the films grown from Zr(pd)4 and Zr(tbob)4 are not well crystallized, and display cracks. These differences in the observed microstructure may be attributed to the different chemical decomposition pathways of the precursors during the film growth, which influence the nucleation and the growth processes. This is also evidenced by the different kinetics of growth from these three precursors under otherwise identical CVD conditions. The details of thin film deposition, and film microstructure analysis by XRD and SEM is presented. The dielectric behavior of the films deposited from different precursors, as studied by C-V measurements, are compared.

Morphology and thermal characteristics of nano-sized Pb–Sn inclusions in Al

Nanoembedded aluminum alloys with bimetallic dispersoids of Sn and Pb of compositions Sn82–Pb18, Sn64–Pb36, and Sn54–Pb46 were synthesized by rapid solidification. The two phases, face-centered-cubic Pb and tetragonal Sn solid-solution, coexist in all the particles. The crystallographic relation between the two phases and the matrix depends upon the solidification pathways adopted by the particles. For Al–(Sn82–Pb18), we report a new orientation relation given by [011]Al//[010]Sn and (o11)A1//(101)Sn. Pb exhibits a cube-on-cube orientation with Al in few particles, while in others no orientation relationship could be observed. In contrast, Pb in Sn64–Pb36 and Sn54–Pb46 particles always exhibits cube-on-cube orientation with the matrix. Sn does not show any orientation relationship with Al or Pb in these cases. Differential scanning calorimetry studies revealed melting at eutectic temperature for all compositions, although solidification pathways are different. Attempts were made to correlate these with the melting and heterogeneous nucleation characteristics.

Lead Stereochemistry in Incommensurate Ferroelectric Perovskites and in Incommensurate Lead Monoxide

We have performed Rietveld refinements on neutron and synchrotron diffraction patterns and density functional calculations on various ferroelectric lead perovskites and on α lead monoxide (litharge). These structural data have allowed to shed some light on lead stereochemistry in these compounds. In particular, we discuss the changing in the lead behaviour between the paraelectric cubic phases and the low temperature anti or ferroelectric phases in Pb2CoWO6 and Pb2MgTeO6 (both incommensurate), in Pb2MgWO6 (antiferroelectric) and in PbMg1/3Nb2/3O3 (relaxor). The possible phase transition mechanisms are reviewed and the bonds are compared to those in the aperiodic structure of α-lead monoxide.

A Study of Nanostructures of Thin Films in B–C–N System Produced by Pulsed Laser Deposition and Nitrogen Ion-Beam-Assisted Pulsed Laser Deposition

We report the synthesis of thin films of B–C–N and C–N deposited by N+ ion-beam-assisted pulsed laser deposition (IBPLD) technique on glass substrates at different temperatures. We compare these films with the thin films of boron carbide synthesized by pulsed laser deposition without the assistance of ion-beam. Electron diffraction experiments in the transmission electron microscope shows that the vapor quenched regions of all films deposited at room temperature are amorphous. In addition, shown for the first time is the evidence of laser melting and subsequent rapid solidification of B4C melt in the form of micrometer- and submicrometer-size round particulates on the respective films. It is possible to amorphize B4C melt droplets of submicrometer sizes. Solidification morphologies of micrometer-size droplets show dispersion of nanocrystallites of B4C in amorphous matrix within the droplets. We were unable to synthesize cubic carbon nitride using the current technique. However, the formation of nanocrystalline turbostratic carbo- and boron carbo-nitrides were possible by IBPLD on substrate at elevated temperature and not at room temperature. Turbostraticity relaxes the lattice spacings locally in the nanometric hexagonal graphite in C–N film deposited at 600 °C leading to large broadening of diffraction rings.

Role of B2O3 on the phase stability and long phosphorescence of SrAl2O4 : Eu, Dy

The role of B2O3 addition on the long phosphorescence of SrAl2O4:Eu2+, Dy3+ has been investigated. B2O3 is just not an inert high temperature solvent (flux) to accelerate grain growth, according to SEM results. B2O3 has a substitutional effect, even at low concentrations. by way of incorporation of BO4 in the corner-shared AlO4 framework of the distorted 'stuffed' tridymite structure of SrAl2O4. which is discernible from the IR and solid-state MAS NMR spectral data. With increasing concentrations, B2O3 reacts with SrAl2O4 to form Sr4Al4O25 together with Sr-borate (SrB2O4) as the glassy phase, as evidenced by XRD and SEM studies. At high B2O3 contents, Sr4Al14O25 converts to SrAl2B2O7 (cubic and hexagonal), SrAl12O19 and Sr-borate (SrB4O7) glass. Sr4Al14O25:Eu2+, Dy3+ has also been independently synthesized to realize the blue emitting (lambda(em)approximate to490 nm) phosphor. The afterglow decay as well as thermoluminescence studies reveal that Sr4Al14O25:Eu, Dy exhibits equally long phosphorescence as that of SrAl2O4:Eu2+, Dy3+. In both cases, long phosphorescence is noticed only when BO4 is present along with Dy3+ and Eu2+. Here Dy3+ because of its higher charge density than Eu2+ prefers to occupy the Sr sites in the neighbourhood of BO4, as the effective charge on borate is more negative than that of AlO4. Thus. Dy3+ forms a substitutional defect complex with borate and acts as an acceptor-type defect center. These defects Eu2+ ions and the subsequent thermal release of hole at room temperature followed by the trap the hole generated by the excitation of recombination with electron resulting in the long persistent phosphorescence. (C) 2003 Elsevier Science B.V. All rights reserved.

Studies on the structural and ionic transport properties at elevated temperatures of La1-xMnO3 +/-delta synthesized by a wet chemical method

Structural transformation and ionic transport properties are investigated on wet-chemically synthesized La1-xMnO3 (X=0.0-0.18) compositions. Powders annealed in oxygen/air at 1000-1080 K exhibit cubic symmetry and transform to rhombohedral on annealing at 1173-1573 K in air/oxygen. Annealing above 1773 K in air or in argon/helium at 1473 K stabilized distorted rhombohedral or orthorhombic symmetry. Structural transformations are confirmed from XRD and TEM studies. The total conductivity of sintered disks, measured by four-probe technique, ranges from 5 S cm(-1) at 298 K to 105 S cm(-1) at 1273 K. The ionic conductivity measured by blocking electrode technique ranges from 1.0X10(-6) S cm(-1) at 700 K to 2.0X10(-3) S cm(-1) at 1273 K. The ionic transference number of these compositions ranges from 3.0X10(-5) to 5.0X10(-5) at 1273 K. The activation energy deduced from experimental data for ionic conduction and ionic migration is 1.03-1.10 and 0.80-1.00 eV, respectively. The activation energy of formation, association and migration of vacancies ranges from 1.07 to 1.44 eV. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis and photoluminescent properties of ZnS nanocrystals doped with copper and halogen

A novel wet-chemical precipitation method is optimized for the synthesis of ZnS nanocrystals doped with Cu+ and halogen. The nanoparticles were stabilized by capping with polyvinyl pyrrolidone (PVP). XRD studies show the phase singularity of ZnS particles having zinc-blende (cubic) structure. TEM as well as XRD line broadening indicate that the average crystallite size of undoped samples is similar to2 nm. The effects of change in stoichiometry and doping with Cu+ and halogen on the photoluminescence properties of ZnS nanophosphors have been investigated. Sulfur vacancy (Vs) related emission with peak maximum at 434 nm has been dominant in undoped ZnS nanoparticles. Unlike in the case of microcrystalline ZnS phosphor, incorporation of halogens in nanoparticles did not result V-Zn related self-activated emission. However, emission characteristics of nanophosphors have been changed with Cu+ activation due to energy transfer from vacancy centers to dopant centers. The use of halogen as co-activator helps to increase the solubility of Cu+ ions in ZnS lattice and also enhances the donor-acceptor type emission efficiency. With increase in Cu+ doping, Cu-Blue centers (CuZn-Cui+), which were dominant at low Cu+ concentrations, has been transformed into Cu-Green (Cu-Zn(-)) centers and the later is found to be situated near the surface regions of nanoparticles. From these studies we have shown that, by controlling the defect chemistry and suitable doping, photoluminescence emission tunability over a wide wavelength range, i.e., from 434 to 514 nm, can be achieved in ZnS nanophosphors. (C) 2003 Elsevier B.V. All rights reserved.