Inferring the effects of compositional boundary layers on crystal nucleation, growth textures, and mineral chemistry in natural volcanic tephras through submicron-resolution imaging

NASA Astrophysics Data System (ADS)

Zellmer, Georg; Sakamoto, Naoya; Hwang, Shyh-Lung; Matsuda, Nozomi; Iizuka, Yoshiyuki; Moebis, Anja; Yurimoto, Hisayoshi

2016-09-01

Crystal nucleation and growth are first order processes captured in volcanic rocks and record important information about the rates of magmatic processes and chemical evolution of magmas during their ascent and eruption. We have studied glass-rich andesitic tephras from the Central Plateau of the Southern Taupo Volcanic Zone by electron- and ion-microbeam imaging techniques to investigate down to sub-micrometre scale the potential effects of compositional boundary layers (CBLs) of melt around crystals on the nucleation and growth of mineral phases and the chemistry of crystal growth zones. We find that CBLs may influence the types of mineral phases nucleating and growing, and growth textures such as the development of swallowtails. The chemistry of the CBLs also has the capacity to trigger intermittent overgrowths of nanometre-scale bands of different phases in rapidly growing crystals, resulting in what we refer to as cryptic phase zoning. The existence of cryptic phase zoning has implications for the interpretation of microprobe compositional data, and the resulting inferences made on the conditions of magmatic evolution. Identification of cryptic phase zoning may in future lead to more accurate thermobarometric estimates and thus geospeedometric constraints. In future, a more quantitative characterization of CBL formation and its effects on crystal nucleation and growth may contribute to a better understanding of melt rheology and magma ascent processes at the onset of explosive volcanic eruptions, and will likely be of benefit to hazard mitigation efforts.

Antisolvent membrane crystallization of pharmaceutical compounds.

PubMed

Di Profio, Gianluca; Stabile, Carmen; Caridi, Antonella; Curcio, Efrem; Drioli, Enrico

2009-12-01

This article describes a modification of the conventional membrane crystallization technique in which a membrane is used to dose the solvent/antisolvent composition to generate supersaturation and induce crystallization in a drug solution. Two operative configurations are proposed: (a) solvent/antisolvent demixing crystallization, where the solvent is removed in at higher flow rate than the antisolvent so that phase inversion promotes supersaturation and (b) antisolvent addition, in which the antisolvent is dosed into the crystallizing drug solution. In both cases, solvent/antisolvent migration occurs in vapor phase and it is controlled by the porous membrane structure, acting on the operative process parameters. This mechanism is different than that observed when forcing the liquid phases through the pores and the more finely controllable supersaturated environment would generate crystals with the desired characteristics. Two organic molecules of relevant industrial implication, like paracetamol and glycine, were used to test the new systems. Experiments demonstrated that, by using antisolvent membrane crystallization in both configurations, accurate control of solution composition at the crystallization point has been achieved with effects on crystals morphology. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Phase equilibrium modelling of granite magma petrogenesis: B. An evaluation of the magma compositions that result from fractional crystallization

NASA Astrophysics Data System (ADS)

Garcia-Arias, Marcos; Stevens, Gary

2017-04-01

Several fractional crystallization processes (flow segregation, gravitational settling, filter-pressing), as well as batch crystallization, have been investigated in this study using thermodynamic modelling (pseudosections) to test whether they are able to reproduce the compositional trends shown by S-type granites. Three starting compositions comprising a pure melt phase and variable amounts of entrained minerals (0, 20 and 40 wt.% of the total magma) have been used to study a wide range of likely S-type magma compositions. The evolution of these magmas was investigated from the segregation from their sources at 0.8 GPa until emplacement at 0.3 GPa in an adiabatic path, followed by isobaric cooling until the solidus was crossed, in a closed-system scenario. The modelled magmas and the fractionated mineral assemblages are compared to the S-type granites of the Peninsula pluton, Cape Granite Suite, South Africa, which have a composition very similar to most of the S-type granites. The adiabatic ascent of the magmas digests partially the entrained mineral assemblage of the magmas, but unless this entrained assemblage represents less than 1 wt.% of the original magma, part of the mineral fraction survives the ascent up to the chosen pressure of emplacement. At the level of emplacement, batch crystallization produces magmas that only plot within the composition of the granites of the Peninsula pluton if the bulk composition of the original magmas already matched that of the granites. Flow segregation of crystals during the ascent and gravitational settling fractional crystallization produce bodies that are generally more mafic than the most mafic granites of the pluton and the residual melts have an almost haplogranitic composition, producing a bimodal compositional distribution not observed in the granites. Consequently, these two processes are ruled out. Filter-pressing fractional crystallization produces bodies in an onion-layer structure that become more felsic with increasing crystallization, culminating in a haplogranitic melt, and is able to reproduce the compositional trends of the granites, but only if the original magmas already had the composition of the granites. Filter-pressing fractionation produces a mineral assemblage that is 1.5 times more mafic than the magma fraction from which it is derived. However, the mineral assemblages produced by crystallization of an originally pure melt phase are still too felsic to account for the bulk of the granites of the Peninsula pluton. For filter-pressing to produce the most mafic granites of the pluton, the original magmas must already contain an entrained mafic mineral assemblage and have the same composition of the granites, otherwise the modelled trends do not match the maficity (FeO + MgO) or the slope against maficity of the granites. Crystallization of the magma in filter-pressing releases a free water phase, whose amount depends on the amount of water of the original magma, and whose behaviour may be controlled by a water-saturation front. In summary, the main control in the composition of S-type granites is the amount and nature of the entrained mineral assemblage, and filter-pressing fractional crystallization can only modify slightly the compositions of the granitic bodies derived from these magmas.

Synthesis and Screening of Phase Change Chalcogenide Thin Film Materials for Data Storage.

PubMed

Guerin, Samuel; Hayden, Brian; Hewak, Daniel W; Vian, Chris

2017-07-10

A combinatorial synthetic methodology based on evaporation sources under an ultrahigh vacuum has been used to directly synthesize compositional gradient thin film libraries of the amorphous phases of GeSbTe alloys at room temperature over a wide compositional range. An optical screen is described that allows rapid parallel mapping of the amorphous-to-crystalline phase transition temperature and optical contrast associated with the phase change on such libraries. The results are shown to be consistent with the literature for compositions where published data are available along the Sb 2 Te 3 -GeTe tie line. The results reveal a minimum in the crystallization temperature along the Sb 2 Te 3 -Ge 2 Te 3 tie line, and the method is able to resolve subsequent cubic-to-hexagonal phase transitions in the GST crystalline phase. HT-XRD has been used to map the phases at sequentially higher temperatures, and the results are reconciled with the literature and trends in crystallization temperatures. The results clearly delineate compositions that crystallize to pure GST phases and those that cocrystallize Te. High-throughput measurement of the resistivity of the amorphous and crystalline phases has allowed the compositional and structural correlation of the resistivity contrast associated with the amorphous-to-crystalline transition, which range from 5-to-8 orders of magnitude for the compositions investigated. The results are discussed in terms of the compromises in the selection of these materials for phase change memory applications and the potential for further exploration through more detailed secondary screening of doped GST or similar classes of phase change materials designed for the demands of future memory devices.

Effect of Heat Treatment on The Crystal Structur, Electrical Conductivity and Surface of Ba1.5Sr0.5Fe2O5 Composite

NASA Astrophysics Data System (ADS)

Purwanto, P.; Adi, WA; Yunasfi

2017-05-01

The Composite of Ba1,5Sr0,5Fe2O5 has been synthesized by using powder metallurgy technique. The Ba1.5Sr0.5Fe2O5 were prepared from BaCO3, SrCO3 and Fe2O3 raw materials with a specific weight ratio. The three materials were synthesized by powder metallurgy under heat treatment at 800 °C, 900 °C, and 1000 °C for 5 hours. All the three samples were characterized by using X-ray Diffraction (XRD) to determine the crystal structure and crystal size, LCR meter to determine the conductivity, and Scanning Electron Microscope (SEM) to observe the morphological of the composites. The phase analysis result showed that the composite consists of several minor phases such as BaO2, SrO2, and Fe2O3. The Crystal size of composite Ba1.5Sr0.5Fe2O5 decreased while increases the strain of crystal with increasing of sintering temperature. The crystal size of the Ba1.5Sr0.5Fe2O5 composite is 3.55 nm to 7.23 nm and value of strain is 8.47% until 3.90%. Based on the conductivity measurement, it was obtained that the conductivity of the Ba1.5Sr0.5Fe2O5 composite decreased with increasing sintering temperature. It was also noticed that the conductivity increased with increasing of frequency. The conductivity ranged from 6.619×10-7 S/cm to 65.659×10-7 S/cm. The energy dispersive spectroscopy (EDS) analysis showed that several dominant elements were a good agreement with the phase analysis.

Modelling Equilibrium and Fractional Crystallization in the System MgO-FeO-CaO-Al2O3-SiO2

NASA Technical Reports Server (NTRS)

Herbert, F.

1985-01-01

A mathematical modelling technique for use in petrogenesis calculations in the system MgO-FeO-CaO-Al2O3-SiO2 is reported. Semiempirical phase boundary and elemental distribution information was combined with mass balance to compute approximate equilibrium crystallization paths for arbitrary system compositions. The calculation is applicable to a range of system compositions and fractionation calculations are possible. The goal of the calculation is the computation of the composition and quantity of each phase present as a function of the degree of solidification. The degree of solidification is parameterized by the heat released by the solidifying phases. The mathematical requirement for the solution of this problem is: (1) An equation constraining the composition of the magma for each solid phase in equilibrium with the liquidus phase, and (2) an equation for each solid phase and each component giving the distribution of that element between that phase and the magma.

Single crystals of selected titanates and tungstates

NASA Technical Reports Server (NTRS)

Loiacono, G. M.

1972-01-01

The compound preparation and crystal growth of a number of mixed titanate compositions was investigated. None of the compounds studied were found to melt congruently and therefore, crystal growth was extremely difficult. Various single crystal preparation methods always resulted in mixed phases from which 1-2 mm size crystals could be separated. It is concluded from this study that before successful single crystal growth can be accomplished, a detailed study of the phase diagrams in each of the systems of interest must be completed.

Control of composition and crystallinity in hydroxyapatite films deposited by electron cyclotron resonance plasma sputtering

NASA Astrophysics Data System (ADS)

Akazawa, Housei; Ueno, Yuko

2014-01-01

Hydroxyapatite (HAp) films were deposited by electron cyclotron resonance plasma sputtering under a simultaneous flow of H2O vapor gas. Crystallization during sputter-deposition at elevated temperatures and solid-phase crystallization of amorphous films were compared in terms of film properties. When HAp films were deposited with Ar sputtering gas at temperatures above 460 °C, CaO byproducts precipitated with HAp crystallites. Using Xe instead of Ar resolved the compositional problem, yielding a single HAp phase. Preferentially c-axis-oriented HAp films were obtained at substrate temperatures between 460 and 500 °C and H2O pressures higher than 1×10-2 Pa. The absorption signal of the asymmetric stretching mode of the PO43- unit (ν3) in the Fourier-transform infrared absorption (FT-IR) spectra was the narrowest for films as-crystallized during deposition with Xe, but widest for solid-phase crystallized films. While the symmetric stretching mode of PO43- (ν1) is theoretically IR-inactive, this signal emerged in the FT-IR spectra of solid-phase crystallized films, but was absent for as-crystallized films, indicating superior crystallinity for the latter. The Raman scattering signal corresponding to ν1 PO43- sensitively reflected this crystallinity. The surface hardness of as-crystallized films evaluated by a pencil hardness test was higher than that of solid-phase crystallized films.

Growth of copper-zinc and copper-magnesium particles by gas-evaporation technique

NASA Astrophysics Data System (ADS)

Ohno, T.

1984-12-01

Fine particles of Cu-Zn and Cu-Mg systems of diameter less than 500 nm were prepared by evaporating the constituent metals simultaneously from two evaporation sources in an atmosphere of argon of 10 to 30 Torr. The composition, crystal structure and habit of the alloy particles were investigated by electron microscopy. The composition of the alloy particles varied depending on the growth zone of metal smoke and almost all phases known in Cu-Zn or Cu-Mg system were found at the same time. The particles with single phase showed generally well-defined crystal habits characteristic of their crystal structures. For the particles with two phases, a fixed lattice relation between the two phases was generally recognized. The formation process of the alloy particles is discussed through these observations.

Preparation and blood compatibility of polysiloxane/liquid-crystal composite membranes.

PubMed

Li, L; Tu, M; Mou, S; Zhou, C

2001-10-01

Polysiloxane/liquid crystal composite membrane was first suggested to be used as biomaterials. In this work, the polydimethyl-methylhydrosiloxane and polydimethyl-methylethylenesilosiane, as a substrate, were blended with cholesteryl oleyl carbonate (COC) in tetrahydrofuran, and then crosslinked into membranes on glass plates by means of the platinum catalyst at 110 degrees C for 20 min. The effects of the liquid-crystal content in composite membranes on the formation of liquid-crystal phase were verified by the observation of optical polarization microscopy. The relationship between the morphology of the composite membranes and blood compatibility was identified by the dynamic blood-clotting tests, haemolysis ratio measurement, platelet adhesion and SEM observation. The results show that the blood-compatibility of composite membranes with the concentration of liquid crystal 20, 30% (wt) is more excellent than that of other composite membranes.

Enhancement of polar phase and conductivity relaxation in PIL-modified GO/PVDF composites

NASA Astrophysics Data System (ADS)

Xu, Pei; Fu, Weijia; Cui, Zhaopei; Ding, Yunsheng

2018-02-01

To investigate the effect of graphene oxide (GO) modified by polymerized ionic liquid (PIL) on the crystallization and dielectric relaxation of poly(vinylidene fluoride) (PVDF), a series of PVDF composites have been prepared using the solution casting method. The ion-dipole interaction between PIL and >CF2 and the π-dipole interaction between GO and >CF2 can induce synergistically the polar phase, and the π-ion interaction between GO and PIL can strengthen the induction effect of the polar phase and decrease the degree of crystallization of PVDF. The electric modulus and conductivity relaxation are employed to analyze the experimental complex dielectric permittivity. In the frequency spectra of complex permittivity of PVDF composites, space charge polarization and conductivity lead to a large value of dielectric permittivity. The temperature dependence of relaxation time of conductivity relaxation accords with the Arrhenius equation. A low degree of crystallization, more ion concentration, and polar phase in PVDF/PIL/GO enhance the movement of the polymer chain segment and charge carriers.

Influence of crystal phases on electro-optic properties of epitaxially grown lanthanum-modified lead zirconate titanate films

NASA Astrophysics Data System (ADS)

Masuda, Shin; Seki, Atsushi; Masuda, Yoichiro

2010-02-01

We describe here how we have improved the crystal qualities and controlled the crystal phase of the lanthanum-modified lead zirconate titanate (PLZT) film without changing the composition ratio using an oxygen-pressure crystallization process. A PLZT film deposited on a SrTiO3 substrate with the largest electro-optic (EO) coefficient of 498 pm/V has been achieved by controlling the crystal phase of the film. Additionally, a fatigue-free lead zirconate titanate (PZT) capacitor with platinum electrodes has been realized by reducing the oxygen vacancies in the films.

Thermodynamic reactivity, growth and characterization of mercurous halide crystals

NASA Technical Reports Server (NTRS)

Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

1992-01-01

Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

Thermomechanical behavior of shape memory elastomeric composites

NASA Astrophysics Data System (ADS)

Ge, Qi; Luo, Xiaofan; Rodriguez, Erika D.; Zhang, Xiao; Mather, Patrick T.; Dunn, Martin L.; Qi, H. Jerry

2012-01-01

Shape memory polymers (SMPs) can fix a temporary shape and recover their permanent shape in response to environmental stimuli such as heat, electricity, or irradiation. Most thermally activated SMPs use the macromolecular chain mobility change around the glass transition temperature ( Tg) to achieve the shape memory (SM) effects. During this process, the stiffness of the material typically changes by three orders of magnitude. Recently, a composite materials approach was developed to achieve thermally activated shape memory effect where the material exhibits elastomeric response in both the temporary and the recovered configurations. These shape memory elastomeric composites (SMECs) consist of an elastomeric matrix reinforced by a semicrystalline polymer fiber network. The matrix provides background rubber elasticity while the fiber network can transform between solid crystals and melt phases over the operative temperature range. As such it serves as a reversible "switching phase" that enables shape fixing and recovery. Shape memory elastomeric composites provide a new paradigm for the development of a wide array of active polymer composites that utilize the melt-crystal transition to achieve the shape memory effect. This potentially allows for material systems with much simpler chemistries than most shape memory polymers and thus can facilitate more rapid material development and insertion. It is therefore important to understand the thermomechanical behavior and to develop corresponding material models. In this paper, a 3D finite-deformation constitutive modeling framework was developed to describe the thermomechanical behavior of SMEC. The model is phenomenological, although inspired by micromechanical considerations of load transfer between the matrix and fiber phases of a composite system. It treats the matrix as an elastomer and the fibers as a complex solid that itself is an aggregate of melt and crystal phases that evolve from one to the other during a temperature change. As such, the composite consists of an elastomer reinforced by a soft liquid at high temperature and a stiff solid at low temperature. The model includes a kinetic description of the non-isothermal crystallization and melting of the fibers during a temperature change. As the fibers transform from melt to crystal during cooling it is assumed that new crystals are formed in an undeformed state, which requires careful tracking of the kinematics of the evolving phases which comes at a significant computational cost. In order to improve the computational efficiency, an effective phase model (EPM) is adopted to treat the evolving crystal phases as an effective medium. A suite of careful thermomechanical experiments with a SMEC was carried out to calibrate various model parameters, and then to demonstrate the ability of the model to accurately capture the shape memory behavior of the SMEC system during complex thermomechanical loading scenarios. The model also identifies the effects of microstructural design parameters such as the fiber volume fraction.

Effect of gallium alloying on the structure, the phase composition, and the thermoelastic martensitic transformations in ternary Ni-Mn-Ga alloys

NASA Astrophysics Data System (ADS)

Belosludtseva, E. S.; Kuranova, N. N.; Marchenkova, E. B.; Popov, A. G.; Pushin, V. G.

2016-04-01

The effect of gallium alloying on the structure, the phase composition, and the properties of quasibinary Ni50Mn50- z Ga z (0 ⩽ z ⩽ 25 at %) alloys is studied over a wide temperature range. The influence of the alloy composition on the type of crystal structure in high-temperature austenite and martensite and the critical martensitic transformation temperatures is analyzed. A general phase diagram of the magnetic and structural transformations in the alloys is plotted. The temperature-concentration boundaries of the B2 and L21 superstructures in the austenite field, the tetragonal L10 (2 M) martensite, and the 10 M and 14 M martensite phases with complex multilayer crystal lattices are found. The predominant morphology of martensite is shown to be determined by the hierarchy of the packets of thin coherent lamellae of nano- and submicrocrystalline crystals with planar habit plane boundaries close to {011} B2. Martensite crystals are twinned along one of the 24 24{ {011} }{< {01bar 1} rangle _{B2}} "soft" twinning shear systems, which provides coherent accommodation of the martensitic transformation-induced elastic stresses.

Crystallization Behavior of the CaO-Al2O3-MgO System Studied with a Confocal Laser Scanning Microscope

NASA Astrophysics Data System (ADS)

Jung, Sung Suk; Sohn, Il

2012-12-01

The crystallization behavior of a calcium-aluminate system with various MgO content from 2.5 to 7.5 wt pct and CaO/Al2O3 ratios between 0.8 and 1.2 has been examined using a confocal laser scanning microscope (CLSM). CCT (continuous cooling transformation) and time temperature transformation (TTT) diagrams were constructed to identify the primary crystal phase of slag at different compositions and at cooling rates between 25 and 800 K/minutes. In the slag at a CaO/Al2O3 ratio of 1.0, crystallization temperature increased during isothermal and continuous cooling with higher MgO content, and the shortest incubation time was observed at 5 wt pct MgO. When MgO content was fixed to be 5 wt pct, crystallization temperature increased with lower CaO/Al2O3 ratio. According to the slag composition, cooling rates and temperature, the primary phase could be CA, or C5A3, or C3A, or C3MA2, or MgO, and the crystal morphology changes from dendrites to faceted crystals to columnar crystals in this composition range.

Crystallization studies and dielectric properties of (Ba0.7Sr0.3)TiO3 in bariumaluminosilicate glass

NASA Astrophysics Data System (ADS)

Divya, P. V.; Vignesh, G.; Kumar, V.

2007-12-01

Ferroelectric glass-ceramics with a basic composition (1 - y)(Ba0.70Sr0.30)TiO3 : y(BaO : Al2O3 : 2SiO2) have been synthesized by the sol-gel method. The major crystalline phase is the perovskite. The crystallization of the ferroelectric phase in the glass matrix have been studied using differential thermal analysis and x-ray diffraction and the kinetic parameters characterizing the crystallization have been determined using an Arrhenius model. Glass contents <= 5 mol% promoted liquid phase sintering, which reduced the sintering temperature to 1250 °C. The dielectric permittivity of the glass-ceramic samples decreased and the ferroelectric-paraelectric phase transition became more diffuse with increasing glass content. The dielectric connectivity of the ferroelectric phase in the composite have also been investigated and are reported.

Effect of phase composition on crystal texture formation in hot deformed nanocrystalline SmCo5 magnets

NASA Astrophysics Data System (ADS)

Ma, Qiang; Yue, Ming; Xu, Xiaochang; Zhang, Hongguo; Zhang, Dongtao; Zhang, Xuefeng; Zhang, Jiuxing

2018-05-01

In the present study, bulk anisotropic nanocrystalline SmCo5 magnets were prepared by hot press and subsequent hot deformation method. Effect of phase composition on texture and magnetic properties are presented, based on which the mechanism of plastic deformation and texture formation during the hot deformation process is discussed. The SmCo5 magnets were prepared by hot deformation, excessive Sm of 2.5 wt% and 10 wt% was added to compensate the weight loss due to Sm evaporation. Our analyses reveal that the phase composition is one of the most important parameters that determine the texture of SmCo5 magnets. It is therefore suggested that the existence of 2:17 phase and its phase transformation undermined the crystal texture formation as well as the magnetic properties of nanocrystalline SmCo5 magnets.

Chemical resistance and cleanability of glazed surfaces

NASA Astrophysics Data System (ADS)

Hupa, Leena; Bergman, Roger; Fröberg, Linda; Vane-Tempest, Stina; Hupa, Mikko; Kronberg, Thomas; Pesonen-Leinonen, Eija; Sjöberg, Anna-Maija

2005-06-01

Adhesion of soil on glazed surfaces and their cleanability depends on chemical composition, phase composition, and roughness of the surface. The surface can be glossy consisting mainly of a smooth glassy phase. A matt and rough surface consists of a glassy phase and one or more crystalline phases. The origin and composition of the crystalline phases affect the chemical resistance and the cleanability of the surface. Fifteen experimental glossy and matt glazes were soaked in a slightly alkaline cleaning agent solution. The surfaces were spin-coated with sebum, i.e. a soil component typical for sanitary facilities. After wiping out the soil film in a controlled manner, the surface conditions and the soil left were evaluated with colour measurements, SEM/EDXA and COM. The results show that wollastonite-type crystals in the glaze surfaces were attacked in aqueous solutions containing typical cleaning agents. This corrosion led to significant decrease in the cleanability of the surface. The other crystal types observed, i.e. diopside and quartz crystals were not corroded, and the cleanability of glazes containing only these crystals was not changed in the cleaning agent exposures. Also the glassy phase was found to be attacked in some formulations leading to a somewhat decreased cleanability. The repeated soiling and cleaning procedures indicated that soil is accumulated on rough surfaces and surfaces which were clearly corroded by the cleaning agent.

A New Titanium-Bearing Calcium Aluminosilicate Phase. 1; Meteoritic Occurrences and Formation in Synthetic Systems

NASA Technical Reports Server (NTRS)

Paque, Julie M.; Beckett, John R.; Barber, David J.; Stolper, Edward M.

1994-01-01

A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed "UNK," is Ca3Ti(AlTi)2(Si,Al)3O14, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystals oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 C/h from maximum (initial) temperatures of 1375 to 1580 C. Only below 1190 C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic LINK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti (7-13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAls, although glass, which is typically associated with synthetic UN& is not observed in meteoritic occurrences. A low Ti end-member of UNK ("Si-UNK") with a composition new that of Ca3Al2Si4O14 was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.

A new titanium-bearing calcium aluminosilicate phase. 1: Meteoritic occurrences and formation in synthetic systems

NASA Technical Reports Server (NTRS)

Paque, Julie M.; Beckett, John R.; Barber, David J.; Stolper, Edward M.

1994-01-01

A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed 'UNK,' is Ca3Ti(Al,Ti)2(Si,Al)3O14, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystal oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 C/h from maximum (initial) temperatures of 1375 to 1580 C. Only below 1190 C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic UNK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti(7-13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAIs, although glass, which is typically associated with synthetic UNK, is not observed in the meteoritic occurrences. A low Ti end-member of UNK ('Si-UNK') with a composition near that of Ca3Al2Si4O14 was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.

Crystallization of lithium borate glasses

NASA Technical Reports Server (NTRS)

Goktas, A. A.; Neilson, G. F.; Weinberg, M. C.

1992-01-01

The glass-forming ability and crystallization behavior of lithium borate compositions, in the diborate-to-metaborate-range, were studied. In particular, the nature and sequence of formation of crystalline phases and the tendency toward devitrification were investigated as functions of temperature, thermal history and batch composition. It was found that the sequence of crystalline phase formation was sensitive to all of the three latter factors, and it was observed that under certain conditions metastable defect structures of the metaborate can appear.

Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

NASA Technical Reports Server (NTRS)

Wiesner, Valerie L.; Bansal, Narottam P.

2015-01-01

The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

Crystallization and growth of Ni-Si alloy thin films on inert and on silicon substrates

NASA Astrophysics Data System (ADS)

Grimberg, I.; Weiss, B. Z.

1995-04-01

The crystallization kinetics and thermal stability of NiSi2±0.2 alloy thin films coevaporated on two different substrates were studied. The substrates were: silicon single crystal [Si(100)] and thermally oxidized silicon single crystal. In situ resistance measurements, transmission electron microscopy, x-ray diffraction, Auger electron spectroscopy, and Rutherford backscattering spectroscopy were used. The postdeposition microstructure consisted of a mixture of amorphous and crystalline phases. The amorphous phase, independent of the composition, crystallizes homogeneously to NiSi2 at temperatures lower than 200 °C. The activation energy, determined in the range of 1.4-2.54 eV, depends on the type of the substrate and on the composition of the alloyed films. The activation energy for the alloys deposited on the inert substrate was found to be lower than for the alloys deposited on silicon single crystal. The lowest activation energy was obtained for nonstoichiometric NiSi2.2, the highest for NiSi2—on both substrates. The crystallization mode depends on the structure of the as-deposited films, especially the density of the existing crystalline nuclei. Substantial differences were observed in the thermal stability of the NiSi2 compound on both substrates. With the alloy films deposited on the Si substrate, only the NiSi2 phase was identified after annealing to temperatures up to 800 °C. In the films deposited on the inert substrate, NiSi and NiSi2 phases were identified when the Ni content in the alloy exceeded 33 at. %. The effects of composition and the type of substrate on the crystallization kinetics and thermal stability are discussed.

Crystal-Chemical Analysis Martian Minerals in Gale Crater

NASA Technical Reports Server (NTRS)

Morrison, S. M.; Downs, R. T.; Blake, D. F.; Bish, D. L.; Ming, D. W.; Morris, R. V.; Yen, A. S.; Chipera, S. J.; Treiman, A. H.; Vaniman, D. T.;

Neutron scattering as a probe of liquid crystal polymer-reinforced composite materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hjelm, R.P.; Douglas, E.P.; Benicewicz, B.C.

1995-12-31

This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This research project sought to obtain nanoscale and molecular level information on the mechanism of reinforcement in liquid crystal polymer (LCP)-reinforced composites, to realize molecular-reinforced LCP composites, and to test the validity of the concept of molecular reinforcement. Small-angle neutron scattering was used to study the structures in the ternary phase diagram of LCP with liquid crystal thermosets and solvent on length scales ranging from 1-100 nm. The goal of the scattering measurements is to understand the phase morphologymore » and degree of segregation of the reinforcing and matrix components. This information helps elucidate the physics of self assembly in these systems. This work provides an experimental basis for a microengineering approach to composites of vastly improved properties.« less

The Use of Atomic-Force Microscopy for Studying the Crystallization Process of Amorphous Alloys

NASA Astrophysics Data System (ADS)

Elmanov, G. N.; Ivanitskaya, E. A.; Dzhumaev, P. S.; Skrytniy, V. I.

The crystallization process of amorphous alloys is accompanied by the volume changes as a result of structural phase transitions. This leads to changes in the surface topography, which was studied by atomic force microscopy (AFM). The changes of the surface topography, structure and phase composition during multistage crystallization process of the metallic glasses with composition Ni71,5Cr6,8Fe2,7B11,9Si7,1 and Ni63,4Cr7,4Fe4,3Mn0,8B15,6Si8,5 (AWS BNi2) has been investigated. The obtained results on changing of the surface topography in crystallization process are in good agreement with the data of X-ray diffraction analysis (XRD). The nature of redistribution of some alloy components in the crystallization process has been suggested.

Formation of the Structure of a Eutectic Alloy of the Nb - Si System During Directed Crystallization with Liquid-Metal Coolant

NASA Astrophysics Data System (ADS)

Bondarenko, Yu. A.; Echin, A. B.; Kolodyazhnyi, M. Yu.; Surova, V. A.

2017-11-01

Peculiarities of the structure of a refractory eutectic alloy of the Nb - Si system, formed by the method of directed crystallization with liquid-metal coolant, have been studied. Characteristic zones of microstructure of the ingot obtained upon directed crystallization are considered, the alloy composition is analyzed, and volume fractions of phases in the Nb - Si composite are determined.

Crystallization kinetics of Mg–Cu–Yb–Ca–Ag metallic glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsarkov, Andrey A., E-mail: tsarkov@misis.ru; WPI Advanced Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577; Zanaeva, Erzhena N.

The paper presents research into a Mg–Cu–Yb system based metallic glassy alloys. Metallic glasses were prepared using induction melting and further injection on a spinning copper wheel. The effect of alloying by Ag and Ca on the glass forming ability and the kinetics of crystallization of Mg–Cu–Yb system based alloys were studied. The differential scanning calorimeter and X-ray diffractometer were used to investigate the kinetics of crystallization and the phase composition of the samples. An indicator of glass forming ability, effective activation energy of crystallization, and enthalpy of mixing were calculated. An increase of the Ca and Ag content hasmore » a positive effect on the glass forming ability, the effective activation energy of crystallization, and the enthalpy of mixing. The highest indicators of the glass forming ability and the thermal stability were found for alloys that contain both alloying elements. The Ag addition suppresses precipitation of the Mg{sub 2}Cu phase during crystallization. A dual-phase glassy-nanocrystalline Mg structure was obtained in Mg{sub 65}Cu{sub 25}Yb{sub 10} and Mg{sub 59.5}Cu{sub 22.9}Yb{sub 11}Ag{sub 6.6} alloys after annealing. Bulk samples with a composite glassy-crystalline structure were obtained in Mg{sub 59.5}Cu{sub 22.9}Yb{sub 11}Ag{sub 6.6} and Mg{sub 64}Cu{sub 21}Yb{sub 9.5}Ag{sub 5.5} alloys. A thermodynamic database for the Mg–Cu–Yb–Ca–Ag system was created to compare the process of crystallization of alloys with polythermal sections of the Mg–Cu–Yb–Ca–Ag phase diagram. - Highlights: • New alloy compositions based on Mg–Cu–Yb system were developed and investigated. • Increasing content of Ag and Ca leads to improving GFA. • Bulk samples with a composite glassy-crystalline structure were obtained. • Thermodynamic database for Mg–Cu–Yb–Ca–Ag system was created.« less

Linear electro-optic properties of relaxor-based ferroelectric 0.24Pb(In1/2Nb1/2)O3-(0.76 − x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals

PubMed Central

Wu, Fengmin; Yang, Bin; Sun, Enwei; Liu, Gang; Tian, Hao; Cao, Wenwu

2013-01-01

Linear electro-optic properties of 0.24Pb(In1/2Nb1/2)O3-(0.76 − x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals, with compositions in the rhombohedral, morphotropic phase boundary (MPB) and tetragonal phases, have been investigated. Very large effective electro-optic coefficient γc (204 pm/V) was observed in a crystal with the MPB composition when it is poled along [001]. The rhombohedral phase (x = 0.27 and 0.30) single crystals poled along [111] direction and tetragonal phase (x = 0.39) single crystal poled along [001] direction are in single domain, and their electro-optic coefficients (γc = 76, 94, and 43 pm/V for the crystals with x = 0.27, 0.30, and 0.39, respectively) were found to be much higher than that of traditional electro-optic single crystal LiNbO3 (γc = 19.9 pm/V). The electro-optic coefficients of the single crystal in the rhombohedral phase have excellent temperature stability in the experimental temperature range of 10–40 °C. The half-wave voltage Vπ was calculated to be much lower (less than 1000 V) than that of LiNbO3 single crystal (2800 V). These superior properties make the ternary relaxor-PT single crystals very promising for electro-optic modulation applications. PMID:23922449

The role of magma mixing/mingling and cumulate melting in the Neapolitan Yellow Tuff caldera-forming eruption (Campi Flegrei, Southern Italy)

NASA Astrophysics Data System (ADS)

Forni, Francesca; Petricca, Eleonora; Bachmann, Olivier; Mollo, Silvio; De Astis, Gianfilippo; Piochi, Monica

2018-06-01

Understanding the mechanisms responsible for the generation of chemical gradients in high-volume ignimbrites is key to retrieve information on the processes that control the maturation and eruption of large silicic magmatic reservoirs. Over the last 60 ky, two large ignimbrites showing remarkable zoning were emplaced during caldera-forming eruptions at Campi Flegrei (i.e., Campanian Ignimbrite, CI, 39 ka and Neapolitan Yellow Tuff, NYT, 15 ka). While the CI displays linear compositional, thermal and crystallinity gradients, the NYT is a more complex ignimbrite characterized by crystal-poor magmas ranging in composition from trachy-andesites to phonolites. By combining major and trace element compositions of matrix glasses and mineral phases from juvenile clasts located at different stratigraphic heights along the NYT pyroclastic sequence, we interpret such compositional gradients as the result of mixing/mingling between three different magmas: (1) a resident evolved magma showing geochemical characteristics of a melt extracted from a cumulate mush dominated by clinopyroxene, plagioclase and oxides with minor sanidine and biotite; (2) a hotter and more mafic magma from recharge providing high-An plagioclase and high-Mg clinopyroxene crystals and (3) a compositionally intermediate magma derived from remelting of low temperature mineral phases (i.e., sanidine and biotite) within the cumulate crystal mush. We suggest that the presence of a refractory crystal mush, as documented by the occurrence of abundant crystal clots containing clinopyroxene, plagioclase and oxides, is the main reason for the lack of erupted crystal-rich material in the NYT. A comparison between the NYT and the CI, characterized by both crystal-poor extracted melts and crystal-rich magmas representing remobilized portions of a "mature" (i.e., sanidine dominated) cumulate residue, allows evaluation of the capability of crystal mushes of becoming eruptible upon recharge.

Materials research at Stanford University. [composite materials, crystal structure, acoustics

NASA Technical Reports Server (NTRS)

1975-01-01

Research activity related to the science of materials is described. The following areas are included: elastic and thermal properties of composite materials, acoustic waves and devices, amorphous materials, crystal structure, synthesis of metal-metal bonds, interactions of solids with solutions, electrochemistry, fatigue damage, superconductivity and molecular physics and phase transition kinetics.

Raman spectroscopic investigations on natural samples from the Integrated Ocean Drilling Program (IODP) Expedition 311: indications for heterogeneous compositions in hydrate crystals.

PubMed

Schicks, J M; Ziemann, M A; Lu, H; Ripmeester, J A

2010-12-01

Natural gas hydrates usually are found in the form of structure I, encasing predominantly methane in the hydrate lattices as guest molecules, sometimes also minor amount of higher hydrocarbons, CO2 or H2S. Raman spectroscopy is an approved tool to determine the composition of the hydrate phase. Thus, in this study Raman spectroscopic analyses have been applied to hydrate samples obtained from Integrated Ocean Drilling Program (IODP) Expedition 311 in two different approaches: studying the samples randomly taken from the hydrate core, and--as a new application--mapping small areas on the surface of clear hydrate crystals. The results obtained imply that the gas composition of hydrate, in terms of relative concentrations of CH4 and H2S, is not homogeneous over a core or even within a crystal. The mapping method yielded results with very high lateral resolution, indicating the coexistence of different phases with the same structure but different compositions within a hydrate crystal. Copyright © 2010 Elsevier B.V. All rights reserved.

Interaction between Convection and Heat Transfer in Crystal Growth

NASA Technical Reports Server (NTRS)

1998-01-01

Crystals are integral components in some of our most sophisticated and rapidly developing industries. Single crystals are solids with the most uniform structures that can be obtained on an atomic scale. Because of their structural uniformity, crystals can transmit acoustic and electromagnetic waves and charged particles with essentially no scattering or interferences. This transparency, which can be selectively modified by controlled additions of impurities known as dopants, is the foundation of modern electronic industry. It has brought about widespread application of crystals in transistors, lasers, microwave devices, infrared detectors, magnetic memory devices, and many other magnets and electro-optic components. The performance of a crystal depends strongly on its compositional homogeneity. For instance, in modern microcircuitry, compositional variations of a few percent (down to a submicron length scale) can seriously jeopardize predicted yields. Since crystals are grown by carefully controlled phase transformations, the compositional adjustment in the solid is often made during growth from the nutrient. Hence, a detailed understanding of mass transfer in the nutrient is essential. Moreover, since mass transfer is often the slowest process during growth, it is usually the rate limiting mechanism. Crystal growth processes are usually classified according to the nature of the parent phase. Nevertheless, whether the growth occurs by solidification from a melt (melt growth), nucleation from a solution (solution growth), condensation from a vapor (physical vapor transport) or chemical reaction of gases (chemical vapor deposition), the parent phase is a fluid. As is with most non-equilibrium processes involving fluids, liquid or vapor, fluid motion plays an important role, affecting both the concentration and temperature gradients at the soli-liquid interface.

Crucibleless crystal growth and Radioluminescence study of calcium tungstate single crystal fiber

NASA Astrophysics Data System (ADS)

Silva, M. S.; Jesus, L. M.; Barbosa, L. B.; Ardila, D. R.; Andreeta, J. P.; Silva, R. S.

2014-11-01

In this article, single phase and high optical quality scheelite calcium tungstate single crystal fibers were grown by using the crucibleless laser heated pedestal growth technique. The as-synthesized calcium tungstate powders used for shaping seed and feed rods were investigated by X-ray diffraction technique. As-grown crystals were studied by Raman spectroscopy and Radioluminescence measurements. The results indicate that in both two cases, calcined powder and single crystal fiber, only the expected scheelite CaWO4 phase was observed. It was verified large homogeneity in the crystal composition, without the presence of secondary phases. The Radioluminescence spectra of the as-grown single crystal fibers are in agreement with that present in Literature for bulk single crystals, presented a single emission band centered at 420 nm when irradiated with β-rays.

Experimental Studies on Mass Transport of Cadmium-Zinc Telluride by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Palosz, W.; Szofran, F. R.; Lehoczky, S. L.

1995-01-01

Experimental studies on mass transport of ternary compound, Cd(1-x)Zn(x)Te by physical vapor transport (PVT) for source compositions up to X = 0.21 are presented. The effect of thermochemical (temperatures, vapor composition) and other factors (preparation of the source, crystal growth rate, temperature gradient) on composition and composition profiles of the grown crystals were investigated. A steep decrease in the mass flux with an increase in X(crystal) for X less than 0.1, and a difference in composition between the source and the deposited material have been observed. The composition profiles of the crystals were found to depend on the density and pretreatment of the source, and on the temperature gradient in the source zone. The homogeneity of the crystals improves at low undercoolings and/or when an appropriate excess of metal constituents is present in the vapor phase. The experimental results are in good agreement with our thermochemical model of this system.

Experimental determination of phase relationships of a chemically-zoned peralkaline silicic reservoir: the example of Green Tuff eruption at Pantelleria (Italy)

NASA Astrophysics Data System (ADS)

Romano, Pierangelo; Andujar, Joan; Scaillet, Bruno; Rotolo, Silvio

2017-04-01

Phase equilibrium experiments are recognized as an excellent method to determine the pre-eruptive conditions of magmas inasmuch they are extremely sensitive to small variation in major elements composition in the studied rocks. Trachytes and peralkaline rhyolites (i.e pantellerite and comendite) usually represent the felsic end-member in continental rift systems and oceanic island settings. Pantelleria island, almost entirely made up of trachyte and pantellerite, is well known in the petrological literature as being the type locality of pantellerites. In this study we present the results of phase equilibrium experiments performed on representative peralkaline rhyolite (pantellerite) and metaluminous trachytes of the Green Tuff eruptions of Pantelleria, the sole known compositionally zoned ignimbrite at this volcanic location, which varies from a crystal-poor pantellerite at the base towards a crystal-rich trachyte at the top of the eruptive sequence. Crystallization experiments were performed in the temperature range 750-950°C, pressure 1-1.5 kbar, fluid saturation conditions with XH2O (=H2O/H2O+CO2) between 0 and 1 and redox conditions fixed around the FMQ (Fayalite-Magnetite- Quartz) buffer. Results show that at 900 °C pantelleritic starting compositions are well above their liquidus, regardless their water content. At T < 800°C clinopyroxene is the liquidus phase followed by amphibole and alkali feldspar. Aenigmatite and quartz crystallize at 750°C and XH2O lower than 0.8. In contrast, the trachytic composition at 800°C is highly crystallized regardless its water content. The liquidus phase is clinopyroxene crystallizing at 950°C and XH2O<0.8 followed by iron-rich olivine and alkali feldspar. Iron-bearing minerals record the effect of both H2O and fO2, showing progressive iron enrichment when XH2O decreases. Alkali feldspar becomes the most abundant mineral phase for XH2O<0.8 at 900°C or XH2O<1 at 850°C both at 1 and 1.5 kbar. Experiments reproduced the mineral assemblages of the natural rocks, i.e. the pre-eruptive conditions were constrained at P 1 kbar, and is found that the compositional zoning in magma chamber (pantellerite to trachyte) is related to a temperature gradient (750°C-900°) within the reservoir. Moreover, our results allow demonstrating that a peralkaline liquid derivate can be produced from a metaluminous trachyte at T< 850°C after extensive alkali feldspar crystallization ( 80 wt%).

Phase Equilibria and Crystal Chemistry in Portions of the System SrO-CaO-Bi2O3-CuO, Part II—The System SrO-Bi2O3-CuO

PubMed Central

Roth, R. S.; Rawn, C. J.; Burton, B. P.; Beech, F.

1990-01-01

New data are presented on the phase equilibria and crystal chemistry of the binary systems Sr0-Bi203 and SrO-CuO and the ternary system SrO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurements are reported for all the binary SrO-Bi2O3 phases, including a new phase identified as Sr6Bi2O9. The ternary system contains at least four ternary phases which can be formed in air at ~900 °C. These are identified as Sr2Bi2CuO6, Sr8Bi4Cu5O19+x, Sr3Bi2Cu2O8 and a solid solution (the Raveau phase) which, for equilibrium conditions at ~900 °C, corresponds approximately to the formula Sr1.8−xBi2.2+xCu1±x/2Oz.(0.0⩽x⩽~0.15). Superconductivity in this phase apparently occurs only in compositions that correspond to negative values of x. Compositions that lie outside the equilibrium Raveau-phase field often form nearly homogeneous Raveau-phase products. Typically this occurs after relatively brief heat treatments, or in crystallization of a quenched melt. PMID:28179779

Sintering and crystallization behavior of CaMgSi{sub 2}O{sub 6}-NaFeSi{sub 2}O{sub 6} based glass-ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goel, Ashutosh; Kansal, Ishu; Dipartimento di Ingegneria dei Materiali e dell'Ambiente, Facolta di Ingegneria, Universita di Modena e Reggio Emilia, 41100 Modena

2009-11-01

We report on the synthesis, sintering, and crystallization behaviors of a glass with a composition corresponding to 90 mol % CaMgSi{sub 2}O{sub 6}-10 mol % NaFeSi{sub 2}O{sub 6}. The investigated glass composition crystallized superficially immediately after casting of the melt and needs a high cooling rate (rapid quenching) in order to produce an amorphous glass. Differential thermal analysis and hot-stage microscopy were employed to investigate the glass forming ability, sintering behavior, relative nucleation rate, and crystallization behavior of the glass composition. The crystalline phase assemblage in the glass-ceramics was studied under nonisothermal heating conditions in the temperature range of 850-950more » deg. C in both air and N{sub 2} atmosphere. X-ray diffraction studies adjoined with the Rietveld-reference intensity ratio method were employed to quantify the amount of crystalline phases, while electron microscopy was used to shed some light on the microstructure of the resultant glass-ceramics. Well sintered glass-ceramics with diopside as the primary crystalline phase were obtained where the amount of diopside varied with the heating conditions.« less

KREEP basalt petrogenesis: Insights from 15434,181

NASA Astrophysics Data System (ADS)

Cronberger, Karl; Neal, Clive R.

2017-05-01

Returned lunar KREEP basalts originated through impact processes or endogenous melting of the lunar interior. Various methods have been used to distinguish between these two origins, with varying degrees of success. Apollo 15 KREEP basalts are generally considered to be endogenous melts of the lunar interior. For example, sample 15434,181 is reported to have formed by a two-stage cooling process, with large orthopyroxene (Opx) phenocrysts forming first and eventually cocrystalizing with smaller plagioclase crystals. However, major and trace element analyses of Opx and plagioclase coupled with calculated equilibrium liquids are inconsistent with the large orthopyroxenes being a phenocryst phase. Equilibrium liquid rare earth element (REE) profiles are enriched relative to the whole rock (WR) composition, inconsistent with Opx being an early crystallizing phase, and these are distinct from the plagioclase REE equilibrium liquids. Fractional crystallization modeling using the Opx equilibrium liquids as a parental composition cannot reproduce the WR values even with crystallization of late-stage phosphates and zircon. This work concludes that instead of being a phenocryst phase, the large Opx crystals are actually xenocrysts that were subsequently affected by pyroxene overgrowths that formed intergrowths with cocrystallizing plagioclase.

Novel polypropylene/inorganic fullerene-like WS2 nanocomposites containing a β-nucleating agent: isothermal crystallization and melting behavior.

PubMed

Naffakh, Mohammed; Marco, Carlos; Ellis, Gary

2012-02-16

The isothermal crystallization and subsequent melting behavior of isotactic polypropylene (iPP) nucleated with different nucleating agents (NAs) are investigated. Tungsten disulfide (IF-WS(2)) and N,N'-dicyclohexyl-2,6-naphthalene (NJ) and dual-additive mixtures are introduced into an iPP matrix to generate new materials that exhibit variable α- and β-polymorphism. As shown in previous work, small amounts of IF-WS(2) or NJ have a nucleating effect during the crystallization of iPP. However, the isothermal crystallization and melting behavior of iPP nucleated by dual α(IF-WS(2))/β(NJ) additive systems are dependent on both the NA composition balance and the crystallization temperature. In particular, our results demonstrate that it is possible to obtain any α-phase to β-phase content ratio by controlling the composition of NAs under appropriate isothermal crystallization conditions. The nucleating behavior of the additives can be illustrated by competitive nucleation, and the correlation between crystallization and melting temperatures and relative α- and β-crystals content in iPP in the nanocomposites is discussed.

Ba(1-x)Sr(x)Zn2Si2O7--A new family of materials with negative and very high thermal expansion.

PubMed

Thieme, Christian; Görls, Helmar; Rüssel, Christian

2015-12-15

The compound BaZn2Si2O7 shows a high coefficient of thermal expansion up to a temperature of 280 °C, then a transition to a high temperature phase is observed. This high temperature phase exhibits negative thermal expansion. If Ba(2+) is successively replaced by Sr(2+), a new phase with a structure, similar to that of the high temperature phase of BaZn2Si2O7, forms. At the composition Ba0.8Sr0.2Zn2Si2O7, this new phase is completely stabilized. The crystal structure was determined with single crystal X-ray diffraction using the composition Ba0.6Sr0.4Zn2Si2O7, which crystallizes in the orthorhombic space group Cmcm. The negative thermal expansion is a result of motions and distortions inside the crystal lattice, especially inside the chains of ZnO4 tetrahedra. Dilatometry and high temperature X-ray powder diffraction were used to verify the negative thermal expansion. Coefficients of thermal expansion partially smaller than -10·10(-6) K(-1) were measured.

Computer Aided Design of Ni-Based Single Crystal Superalloy for Industrial Gas Turbine Blades

NASA Astrophysics Data System (ADS)

Wei, Xianping; Gong, Xiufang; Yang, Gongxian; Wang, Haiwei; Li, Haisong; Chen, Xueda; Gao, Zhenhuan; Xu, Yongfeng; Yang, Ming

The influence of molybdenum, tungsten and cobalt on stress-rupture properties of single crystal superalloy PWA1483 has been investigated using the simulated calculation of JMatPro software which ha s been widely used to develop single crystal superalloy, and the effect of alloying element on the stability of strengthening phase has been revealed by using the Thermo-Calc software. Those properties calculation results showed that the increasing of alloy content could facilitate the precipitation of TCP phases and increase the lattice misfit between γ and γ' phase, and the effect of molybdenum, tantalum was the strongest and that of cobalt was the weakest. Then the chemical composition was optimized, and the selected compositions showed excellent microstructure stability and stress-rupture properties by the confirmation of d-electrons concept and software calculation.

Method for making glass-ceramic articles exhibiting high frangibility

DOEpatents

Beall, George H.; Brydges, III., William T.; Ference, Joseph; Kozlowski, Theodore R.

1976-02-03

This invention is concerned with glass-ceramic articles having compositions within a very narrowly-delimited area of the MgO-Al.sub.2 O.sub.3 -B.sub.2 O.sub.3 -SiO.sub.2 field and having alpha-quartz and sapphirine as the principal crystal phases, resulting from nucleation through a combination of TiO.sub.2 and ZrO.sub.2. Upon contacting such articles with lithium ions at an elevated temperature, said lithium ions will replace magnesium ions on a two Li.sup.+-for-one Mg.sup..sup.+2 basis within the crystal structures, thereby providing a unitary glass-ceramic article having an integral surface layer wherein the principal crystal phase is a lithium-stuffed beta-quartz solid solution. That transformation of crystal phases results in compressive stresses being set up within the surface layer as the articles are cooled. Through the careful control of composition, crystallization treatment, and the parameters of the replacement reaction in the crystal structures, a tremendous degree of stored elastic energy can be developed within the articles such that they will demonstrate frangibility when fractured but will not exhibit undesirable spontaneous breakage and/or spalling.

Studies of Nucleation, Growth, Specific Heat, and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Croat, T. K.; Gangopadhyay, A.; Holland-Moritz, D.; Hyers, Robert W.; Rathz, Thomas J.; Robinson, Michael B.; Rogers, Jan R.

2001-01-01

Undercooling experiments and thermal physical property measurements of metallic alloys on the International Space Station (ISS) are planned. This recently-funded research focuses on fundamental issues of the formation and structure of highly-ordered non-crystallographic phases (quasicrystals) and related crystal phases (crystal approximants), and the connections between the atomic structures of these phases and those of liquids and glasses. It extends studies made previously by us of the composition dependence of crystal nucleation processes in silicate and metallic glasses, to the case of nucleation from the liquid phase. Motivating results from rf-levitation and drop-tube measurements of the undercooling of Ti/Zr-based liquids that form quasicrystals and crystal approximants are discussed. Preliminary measurements by electrostatic levitation (ESL) are presented.

X-ray diffraction studies of phase transformations in heavy-metal fluoride glasses

NASA Technical Reports Server (NTRS)

Bansal, N. P.; Doremus, R. H.

1985-01-01

Powder X-ray diffraction and differential scanning calorimetry studies of the crystallization properties of five ZrF4-based glass compositions have indicated that the crystalline phase in Zr-Ba-La-Pb fluoride glass is beta-BaZrF6; no such identification of crystal phases was obtainable, however, for the other glasses. Reversible polymorphic phase transformations occur in Zr-Ba-La-Li and Zr-Ba-La-Na fluoride glasses, upon heating to higher temperatures.

Characterization of calcium carbonate crystals in pigeon yolk sacs with different incubation times.

PubMed

Song, Juan; Cheng, Haixia; Shen, Xinyu; Hu, Jingxiao; Tong, Hua

2014-05-01

Calcium carbonate crystals are known to form in the yolk sacs of fertile pigeon eggs at late stages of incubation. The composition and structure of these crystals were investigated, the crystallization environment was inspected, and the physical chemistry constants of the yolk fluid were determined through the incubation period. Polarized light microscopy was used to observe the generation and distribution of calcium carbonate crystals in the yolk sac. In addition, X-ray diffraction was employed to analyze the composition and crystal phase of the yolk sac. A decalcification and deproteination method was established to analyze the ultrastructure and composition of the crystals, as well as the internal relationship between inorganic and organic phases of the crystals. Additionally, scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared spectroscopy were used to evaluate the characteristics of the crystals. Our results demonstrated that the calcium carbonate crystals were mainly composed of vaterite and calcite, with vaterite being the major component. Vaterite, a type of biomaterial generated by an organic template control, presented as a concentric hierarchical spherical structure. The organic nature of the biomaterial prevented vaterite from transforming into calcite, which is more thermodynamically stable than vaterite. Additionally, the configuration, size, and aggregation of vaterite were also mediated by the organic template. This bio-vaterite was found during the incubation period and is valuable in calcium transport during embryonic development. Copyright © 2014 Elsevier Ltd. All rights reserved.

Crystal structure and phase transitions of sodium potassium niobate perovskites

NASA Astrophysics Data System (ADS)

Tellier, J.; Malic, B.; Dkhil, B.; Jenko, D.; Cilensek, J.; Kosec, M.

2009-02-01

This paper presents the crystal structure and the phase transitions of K xNa 1- xNbO 3 (0.4 ≤ x ≤ 0.6). X-ray diffraction measurements were used to follow the change of the unit-cell parameters and the symmetry in the temperature range 100-800 K. At room temperature all the compositions exhibited a monoclinic metric of the unit cell with a small monoclinic distortion (90.32° ≤ β ≤ 90.34°). No major change of symmetry was evidenced in the investigated compositional range, which should be characteristic of the morphotropic phase-boundary region. With increasing temperature, the samples underwent first-order monoclinic-tetragonal and tetragonal-cubic transitions. Only the potassium-rich phases were rhombohedral at 100 K.

Large field-induced-strain at high temperature in ternary ferroelectric crystals

PubMed Central

Wang, Yaojin; Chen, Lijun; Yuan, Guoliang; Luo, Haosu; Li, Jiefang; Viehland, D.

2016-01-01

The new generation of ternary Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 ferroelectric single crystals have potential applications in high power devices due to their surperior operational stability relative to the binary system. In this work, a reversible, large electric field induced strain of over 0.9% at room temperature, and in particular over 0.6% above 380 K was obtained. The polarization rotation path and the phase transition sequence of different compositions in these ternary systems have been determined with increasing electric field applied along [001] direction based on x-ray diffraction data. Thereafter, composition dependence of field-temperature phase diagrams were constructed, which provide compositional and thermal prospectus for the electromechanical properties. It was found the structural origin of the large stain, especially at higher temperature is the lattice parameters modulated by dual independent variables in composition of these ternary solid solution crystals. PMID:27734908

Crystallization of heavy metal fluoride glasses

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Bruce, Allan J.; Doremus, R. H.; Moynihan, C. T.

1984-01-01

The kinetics of crystallization of a number of fluorozirconate glasses were studied using isothermal and dynamic differential scanning calorimetry and X-ray diffraction. The addition of the fluorides LiF, NaF, AlF3, LaF3 to a base glass composition of ZrF4-BaF2 reduced the tendency to crystallize, probably by modifying the viscosity-temperature relation. ZrF4-BaF2-LaF3-AlF3-NaF glass was the most stable against devitrification and perhaps is the best composition for optical fibers with low scattering loss. Some glasses first crystallize out into metastable beta-BaZr2F10 and beta-BaZrF6 phases, which transform into the most stable alpha-phases when heated to higher temperatures. The size of the crystallites was estimated to be about 600 A from X-ray diffraction.

Structural, magnetic, and electrical properties of (1-x)Bi0.85La0.15FeO3-(x)CoFe2O4 multiferroic composites

NASA Astrophysics Data System (ADS)

Pandey, Rabichandra; Pradhan, Lagen Kumar; Kar, Manoranjan

2018-04-01

In this study, the tartaric acid modified sol-gel method was used to synthesize (1-x)Bi0.85La0.15FeO3-(x)CoFe2O4 (BLFO-CFO) composites where x = 0.00, 0.10, 0.20, 0.30, 0.40, and 0.50. The X-ray diffraction (XRD) patterns indicated the formation of composites with both BLFO and CFO crystal symmetry, i.e., perovskite and spinel structures, respectively. Rietveld refinement of the XRD patterns was performed for all of the samples in order to analyze the crystal phases and obtain the structural parameters. There were decreases in the lattice parameters of the perovskite phase as the CFO spinel phase increased in the composites, which may be explained by the strain at the interface of the BLFO and CFO phases. Electrical polarization and dielectric constant enhancements were observed in the BLFO-CFO composites compared with BLFO. The saturation magnetization increased as the CFO phase increased in the composites. The theoretical saturation magnetization (calculated using Vegard's law) was less than the experimentally observed value, possibly due to the spin interaction at the interface of BLFO and CFO.

THE PHYSICAL AND CHEMICAL MICROSTRUCTURE OF THE ACHATINA FULICA EPIPHRAGM.

PubMed

Struthers, M.; Rosair, G.; Buckman, J.; Viney, C.

2002-05-01

Microstructural characterization of Achatina fulica Bowdich, 1822 epiphragms and mucus secretions was performed to address two questions: what are the structure and composition of the reinforcing inorganic phase in the epiphragms, and what enables a durable epiphragm to form quickly in comparison to other biomineralized materials? Characterization was performed by a combination of light microscopy (relying on a variety of contrast modes), wet chemical tests, environmental scanning electron microscopy (including the use of energy dispersive X-ray analysis to obtain compositional data), and X-ray diffraction. The morphology of the inorganic phase promotes mechanical interlocking and presents a large surface for binding to the organic matrix. Strong binding occurs between the organic and inorganic phases. The inorganic phase adopts the calcite structure; its composition is Ca(0.912) Mg(0.088) CO(3). Epiphragms can form quickly because pre-grown crystals of the inorganic reinforcing phase are co-deposited with the mucus matrix. Unlike other biomineralized material, the crystals are not solution-grown in situ on an organic template in the final product.

Study of low-modulus biomedical β Ti-Nb-Zr alloys based on single-crystal elastic constants modeling.

PubMed

Wang, Xing; Zhang, Ligang; Guo, Ziyi; Jiang, Yun; Tao, Xiaoma; Liu, Libin

2016-09-01

CALPHAD-type modeling was used to describe the single-crystal elastic constants of the bcc solution phase in the ternary Ti-Nb-Zr system. The parameters in the model were evaluated based on the available experimental data and first-principle calculations. The composition-elastic properties of the full compositions were predicted and the results were in good agreement with the experimental data. It is found that the β phase can be divided into two regions which are separated by a critical dynamical stability composition line. The corresponding valence electron number per atom and the polycrystalline Young׳s modulus of the critical compositions are 4.04-4.17 and 30-40GPa respectively. Orientation dependencies of single-crystal Young׳s modulus show strong elastic anisotropy on the Ti-rich side. Alloys compositions with a Young׳s modulus along the <100> direction matching that of bone were found. The current results present an effective strategy for designing low modulus biomedical alloys using computational modeling. Copyright © 2016 Elsevier Ltd. All rights reserved.

Phase diagram of the LiNO3-NaNO3-NaCl-Sr(NO3)2 salt system

NASA Astrophysics Data System (ADS)

Rasulov, A. I.; Gasanaliev, A. M.; Mamedova, A. K.; Gamataeva, B. Yu.

2015-04-01

The phase diagram of the quaternary LiNO3-NaNO3-NaCl-Sr(NO3)2 system is studied by means of differential thermal analysis, and the compositions and crystallization temperatures of nonvariant equilibrium phases are revealed. The temperature dependence of conductivity in eutectic and peritectic salt compositions is investigated.

Construction of physical crosslink-based chitosan/liquid crystal composite hydrogel and evaluation on their cytocompatibility

PubMed Central

Du, Lin; Yang, Xiaohui; Li, Wenqiang; Luo, Xuhui; Wu, Hao; Zhang, Jiaqing; Tu, Mei

2017-01-01

In order to provide a novel biomimetic composite substrate for tissue engineering and explore the interaction between cells and this type of material, we developed chitosan/liquid crystal (CS/LC) composite hydrogel with embedded LC phases by composing of cholesterol hydroxypropyl cellulose ester liquid crystalline material and CS. The micromorphology of CS/LC composite hydrogels exhibited ‘islands-sea’ phase separation structures similar to the ‘fluid mosaic model’ of biomembrane. In vitro cell compatibility study suggested that 3T3 is fibroblasts exhibited better initial cell adhesions and higher proliferation rates on the composite hydrogel than on the polystyrene control plate and the pure LC membrane. This novel CS/LC composite hydrogel provides more favorable interface for cell growth and proliferation and may serve as potentially active substrate for engineering interfaces to live cells. PMID:28149528

Crystal phase-based epitaxial growth of hybrid noble metal nanostructures on 4H/fcc Au nanowires

NASA Astrophysics Data System (ADS)

Lu, Qipeng; Wang, An-Liang; Gong, Yue; Hao, Wei; Cheng, Hongfei; Chen, Junze; Li, Bing; Yang, Nailiang; Niu, Wenxin; Wang, Jie; Yu, Yifu; Zhang, Xiao; Chen, Ye; Fan, Zhanxi; Wu, Xue-Jun; Chen, Jinping; Luo, Jun; Li, Shuzhou; Gu, Lin; Zhang, Hua

2018-03-01

Crystal-phase engineering offers opportunities for the rational design and synthesis of noble metal nanomaterials with unusual crystal phases that normally do not exist in bulk materials. However, it remains a challenge to use these materials as seeds to construct heterometallic nanostructures with desired crystal phases and morphologies for promising applications such as catalysis. Here, we report a strategy for the synthesis of binary and ternary hybrid noble metal nanostructures. Our synthesized crystal-phase heterostructured 4H/fcc Au nanowires enable the epitaxial growth of Ru nanorods on the 4H phase and fcc-twin boundary in Au nanowires, resulting in hybrid Au-Ru nanowires. Moreover, the method can be extended to the epitaxial growth of Rh, Ru-Rh and Ru-Pt nanorods on the 4H/fcc Au nanowires to form unique hybrid nanowires. Importantly, the Au-Ru hybrid nanowires with tunable compositions exhibit excellent electrocatalytic performance towards the hydrogen evolution reaction in alkaline media.

An equivalent dipole analysis of PZT ceramics and lead-free piezoelectric single crystals

NASA Astrophysics Data System (ADS)

Bell, Andrew J.

2016-04-01

The recently proposed Equivalent Dipole Model for describing the electromechanical properties of ionic solids in terms of 3 ions and 2 bonds has been applied to PZT ceramics and lead-free single crystal piezoelectric materials, providing analysis in terms of an effective ionic charge and the asymmetry of the interatomic force constants. For PZT it is shown that, as a function of composition across the morphotropic phase boundary, the dominant bond compliance peaks at 52% ZrO2. The stiffer of the two bonds shows little composition dependence with no anomaly at the phase boundary. The effective charge has a maximum value at 50% ZrO2, decreasing across the phase boundary region, but becoming constant in the rhombohedral phase. The single crystals confirm that both the asymmetry in the force constants and the magnitude of effective charge are equally important in determining the values of the piezoelectric charge coefficient and the electromechanical coupling coefficient. Both are apparently temperature dependent, increasing markedly on approaching the Curie temperature.

Phase coexistence and domain configuration in Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 single crystal revealed by synchrotron-based X-ray diffractive three-dimensional reciprocal space mapping and piezoresponse force microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Ruixue; Xu, Han; Yang, Bin

The crystalline phases and domain configuration in the morphotropic phase boundary composition Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 (PMN-0.34PT) single crystal have been investigated by synchrotronbased X-ray 3D Reciprocal Space Mapping (3D-RSM) and Piezoresponse Force Microscopy. The coexistence of tetragonal (T) and monoclinic MC phases in this PMN-0.34PT single crystal is confirmed. The affiliation of each diffraction spot in the 3D-RSM was identified with the assistance of qualitative simulation. Most importantly, the twinning structure between different domains in such a mixed phase PMN-PT crystal is firmly clarified, and the spatial distribution of different twin domains is demonstrated. In addition, the lattice parameters of T andmore » MC phases in PMN-0.34PT single crystal as well as the tilting angles of crystal lattices caused by the interfacial lattice mismatch are determined.« less

Advanced methods for preparation and characterization of infrared detector materials

NASA Technical Reports Server (NTRS)

Broerman, J. G.; Morris, B. J.; Meschter, P. J.

1983-01-01

Crystals were prepared by the Bridgman-Stockbarger method with a wide range of crystal growth rates and temperature gradients adequate to prevent constitutional supercooling under diffusion-limited, steady-state, growth conditions. The longitudinal compositional gradients for different growth conditions and alloy compositions were calculated and compared with experimental data to develop a quantitative model of solute redistribution during the crystal growth of the alloys. Measurements were performed to ascertain the effect of growth conditions on radial compositional gradients. The pseudobinary HgTe-CdTe constitutional phase diagram was determined by precision differential-thermal-analysis measurements and used to calculate the segregation coefficient of Cd as a function of x and interface temperature. Experiments were conducted to determine the ternary phase equilibria in selected regions of the Hg-Cd-Te constitutional phase diagram. Electron and hole mobilities as functions of temperature were analyzed to establish charge-carrier scattering probabilities. Computer algorithms specific to Hg(1-x)CdxTe were developed for calculations of the charge-carrier concentration, charge-carrier mobilities, Hall coefficient, and Dermi Fermi energy as functions of x, temperature, ionized donor and acceptor concentrations, and neutral defect concentrations.

Tunable photonic crystals with partial bandgaps from blue phase colloidal crystals and dielectric-doped blue phases.

PubMed

Stimulak, Mitja; Ravnik, Miha

2014-09-07

Blue phase colloidal crystals and dielectric nanoparticle/polymer doped blue phases are demonstrated to combine multiple components with different symmetries in one photonic material, creating a photonic crystal with variable and micro-controllable photonic band structure. In this composite photonic material, one contribution to the band structure is determined by the 3D periodic birefringent orientational profile of the blue phases, whereas the second contribution emerges from the regular array of the colloidal particles or from the dielectric/nanoparticle-doped defect network. Using the planewave expansion method, optical photonic bands of the blue phase I and II colloidal crystals and related nanoparticle/polymer doped blue phases are calculated, and then compared to blue phases with no particles and to face-centred-cubic and body-centred-cubic colloidal crystals in isotropic background. We find opening of local band gaps at particular points of Brillouin zone for blue phase colloidal crystals, where there were none in blue phases without particles or dopants. Particle size and filling fraction of the blue phase defect network are demonstrated as parameters that can directly tune the optical bands and local band gaps. In the blue phase I colloidal crystal with an additionally doped defect network, interestingly, we find an indirect total band gap (with the exception of one point) at the entire edge of SC irreducible zone. Finally, this work demonstrates the role of combining multiple - by symmetry - differently organised components in one photonic crystal material, which offers a novel approach towards tunable soft matter photonic materials.

Taxonomy of Magma Mixing II: Thermochemistry of Mixed Crystal-Bearing Magmas Using the Magma Chamber Simulator

NASA Astrophysics Data System (ADS)

Bohrson, W. A.; Spera, F. J.; Neilson, R.; Ghiorso, M. S.

2013-12-01

Magma recharge and magma mixing contribute to the diversity of melt and crystal populations, the abundance and phase state of volatiles, and thermal and mass characteristics of crustal magma systems. The literature is replete with studies documenting mixing end-members and associated products, from mingled to hybridized, and a catalytic link between recharge/mixing and eruption is likely. Given its importance and the investment represented by thousands of detailed magma mixing studies, a multicomponent, multiphase magma mixing taxonomy is necessary to systematize the array of governing parameters (e.g., pressure (P), temperature (T), composition (X)) and attendant outcomes. While documenting the blending of two melts to form a third melt is straightforward, quantification of the mixing of two magmas and the subsequent evolution of hybrid magma requires application of an open-system thermodynamic model. The Magma Chamber Simulator (MCS) is a thermodynamic, energy, and mass constrained code that defines thermal, mass and compositional (major, trace element and isotope) characteristics of melt×minerals×fluid phase in a composite magma body-recharge magma-crustal wallrock system undergoing recharge (magma mixing), assimilation, and crystallization. In order to explore fully hybridized products, in MCS, energy and mass of recharge magma (R) are instantaneously delivered to resident magma (M), and M and R are chemically homogenized and thermally equilibrated. The hybrid product achieves a new equilibrium state, which may include crystal resorption or precipitation and/or evolution of a fluid phase. Hundreds of simulations systematize the roles that PTX (and hence mineral identity and abundance) and the mixing ratio (mass of M/mass of R) have in producing mixed products. Combinations of these parameters define regime diagrams that illustrate possible outcomes, including: (1) Mixed melt composition is not necessarily a mass weighted mixture of M and R magmas because crystals may precipitate or resorb. (2) Although a typical expectation is that the mixed magma T is between those of M and R, in some cases, T is lower than both due to the enthalpy cost of mineral resorption. (3) Addition of cooler silicic R to mafic M might be expected to promote crystallization, but in some cases, hybrid melt moves away from phase saturation surface(s) due to compositional effects, and crystallization is suppressed. (4) Addition of R can cause either enhancement or suppression of crystallization, depending on PTX conditions. Phases stable in M may cease to crystallize after mixing, producing a gap in the crystal record. (5) Volatile saturation is likely to be complex, and investigating volatile behavior will help define the thermodynamic states under which mixed magmas may catastrophically vesiculate, perhaps triggering eruption. Use of the magma mixing taxonomy will enhance the ability to quantify key parameters that influence particular magma mixing scenarios and will illuminate MCS enhancements required for handling additional types of magma mixing (e.g., mingling).

Pyroxene thermometry of rhyolite lavas of the Bruneau-Jarbidge eruptive center, Central Snake River Plain

NASA Astrophysics Data System (ADS)

Cathey, Henrietta E.; Nash, Barbara P.

2009-11-01

The Bruneau-Jarbidge eruptive center of the central Snake River Plain in southern Idaho, USA produced multiple rhyolite lava flows with volumes of <10 km 3 to 200 km 3 each from ~11.2 to 8.1 Ma, most of which follow its climactic phase of large-volume explosive volcanism, represented by the Cougar Point Tuff, from 12.7 to 10.5 Ma. These lavas represent the waning stages of silicic volcanism at a major eruptive center of the Yellowstone hotspot track. Here we provide pyroxene compositions and thermometry results from several lavas that demonstrate that the demise of the silicic volcanic system was characterized by sustained, high pre-eruptive magma temperatures (mostly ≥950 °C) prior to the onset of exclusively basaltic volcanism at the eruptive center. Pyroxenes display a variety of textures in single samples, including solitary euhedral crystals as well as glomerocrysts, crystal clots and annealed microgranular inclusions of pyroxene ± magnetite ± plagioclase. Pigeonite and augite crystals are unzoned, and there are no detectable differences in major and minor element compositions according to textural variety — mineral compositions in the microgranular inclusions and crystal clots are identical to those of phenocrysts in the host lavas. In contrast to members of the preceding Cougar Point Tuff that host polymodal glass and mineral populations, pyroxene compositions in each of the lavas are characterized by single rather than multiple discrete compositional modes. Collectively, the lavas reproduce and extend the range of Fe-Mg pyroxene compositional modes observed in the Cougar Point Tuff to more Mg-rich varieties. The compositionally homogeneous populations of pyroxene in each of the lavas, as well as the lack of core-to-rim zonation in individual crystals suggest that individual eruptions each were fed by compositionally homogeneous magma reservoirs, and similarities with the Cougar Point Tuff suggest consanguinity of such reservoirs to those that supplied the polymodal Cougar Point Tuff. Pyroxene thermometry results obtained using QUILF equilibria yield pre-eruptive magma temperatures of 905 to 980 °C, and individual modes consistently record higher Ca content and higher temperatures than pyroxenes with equivalent Fe-Mg ratios in the preceding Cougar Point Tuff. As is the case with the Cougar Point Tuff, evidence for up-temperature zonation within single crystals that would be consistent with recycling of sub- or near-solidus material from antecedent magma reservoirs by rapid reheating is extremely rare. Also, the absence of intra-crystal zonation, particularly at crystal rims, is not easily reconciled with cannibalization of caldera fill that subsided into pre-eruptive reservoirs. The textural, compositional and thermometric results rather are consistent with minor re-equilibration to higher temperatures of the unerupted crystalline residue from the explosive phase of volcanism, or perhaps with newly generated magmas from source materials very similar to those for the Cougar Point Tuff. Collectively, the data suggest that most of the pyroxene compositional diversity that is represented by the tuffs and lavas was produced early in the history of the eruptive center and that compositions across this range were preserved or duplicated through much of its lifetime. Mineral compositions and thermometry of the multiple lavas suggest that unerupted magmas residual to the explosive phase of volcanism may have been stored at sustained, high temperatures subsequent to the explosive phase of volcanism. If so, such persistent high temperatures and large eruptive magma volumes likewise require an abundant and persistent supply of basalt magmas to the lower and/or mid-crust, consistent with the tectonic setting of a continental hotspot.

Czochralski growth of 2 in. Ca3Ta(Ga,Al)3Si2O14 single crystals for piezoelectric applications

NASA Astrophysics Data System (ADS)

Yoshikawa, Akira; Shoji, Yasuhiro; Ohashi, Yuji; Yokota, Yuui; Chani, Valery I.; Kitahara, Masanori; Kudo, Tetsuo; Kamada, Kei; Kurosawa, Shunsuke; Medvedev, Andrey; Kochurikhin, Vladimir

2016-10-01

Growth of 2-in. diameter Al-substituted Ca3TaGa3Si2O14 crystals by Czochralski method is reported. The crystals were grown from the melt of Ca3TaGa1.5Al1.5Si2O14 composition and had langasite structure. No inclusions of secondary phases were detected in these crystals. The Ca3Ta(Ga,Al)3Si2O14 mixed crystals produced using non-substituted Ca3TaGa3Si2O14 seeds were defective. They had cracks and/or poly-crystalline structure. However, those grown on the seed of approximately Ca3TaGa1.5Al1.5Si2O14 composition were defect-free. Phase diagram of the Ca3TaGa3Si2O14-Ca3TaAl3Si2O14 pseudo-binary system and segregation phenomenon are discussed in some details. Homogeneity of the crystals was evaluated by measuring 2D-mapping of leaky surface acoustic wave (LSAW) velocities for Y-cut Ca3TaGa1.5Al1.5Si2O14 substrate. Although some inhomogeneities were observed due to slight variations in chemical composition, the crystal had acceptable homogeneity for applications in acoustic wave devices exhibiting the LSAW velocity variation within ±0.048%.

Characterizing the residual glass in a MgO/Al2O3/SiO2/ZrO2/Y2O3 glass-ceramic

PubMed Central

Seidel, Sabrina; Patzig, Christian; Wisniewski, Wolfgang; Gawronski, Antje; Hu, Yongfeng; Höche, Thomas; Rüssel, Christian

2016-01-01

The non-isochemical crystallization of glasses leads to glass-ceramics in which the chemical composition of the amorphous matrix differs from that of the parent glass. It is challenging to solely analyse the properties of these residual glassy phases because they frequently contain finely dispersed crystals. In this study, the composition of the residual glass matrix after the crystallization of a glass with the mol% composition 50.6 SiO2 · 20.7 MgO · 20.7 Al2O3 · 5.6 ZrO2 · 2.4 Y2O3 is analysed by scanning transmission electron microscopy (STEM) including energy dispersive X-ray analysis (EDXS). A batch of the residual glass with the determined composition is subsequently melted and selected properties are analysed. Furthermore, the crystallization behaviour of this residual glass is studied by X-ray diffraction, scanning electron microscopy including electron backscatter diffraction and STEM-EDXS analyses. The residual glass shows sole surface crystallization of indialite and multiple yttrium silicates while bulk nucleation does not occur. This is in contrast to the crystallization behaviour of the parent glass, in which a predominant bulk nucleation of spinel and ZrO2 is observed. The crystallization of the residual glass probably leads to different crystalline phases when it is in contact to air, rather than when it is enclosed within the microstructure of the parent glass-ceramics. PMID:27734918

CRYSTAL CHEMISTRY OF THREE-COMPONENT WHITE DWARFS AND NEUTRON STAR CRUSTS: PHASE STABILITY, PHASE STRATIFICATION, AND PHYSICAL PROPERTIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engstrom, T. A.; Yoder, N. C.; Crespi, V. H., E-mail: tae146@psu.edu, E-mail: ncy5007@psu.edu, E-mail: vhc2@psu.edu

A systematic search for multicomponent crystal structures is carried out for five different ternary systems of nuclei in a polarizable background of electrons, representative of accreted neutron star crusts and some white dwarfs. Candidate structures are “bred” by a genetic algorithm and optimized at constant pressure under the assumption of linear response (Thomas–Fermi) charge screening. Subsequent phase equilibria calculations reveal eight distinct crystal structures in the T = 0 bulk phase diagrams, five of which are complicated multinary structures not previously predicted in the context of compact object astrophysics. Frequent instances of geometrically similar but compositionally distinct phases give insight into structural preferencesmore » of systems with pairwise Yukawa interactions, including and extending to the regime of low-density colloidal suspensions made in a laboratory. As an application of these main results, we self-consistently couple the phase stability problem to the equations for a self-gravitating, hydrostatically stable white dwarf, with fixed overall composition. To our knowledge, this is the first attempt to incorporate complex multinary phases into the equilibrium phase-layering diagram and mass–radius-composition dependence, both of which are reported for He–C–O and C–O–Ne white dwarfs. Finite thickness interfacial phases (“interphases”) show up at the boundaries between single-component body-centered cubic (bcc) crystalline regions, some of which have lower lattice symmetry than cubic. A second application—quasi-static settling of heavy nuclei in white dwarfs—builds on our equilibrium phase-layering method. Tests of this nonequilibrium method reveal extra phases that play the role of transient host phases for the settling species.« less

Crystal Chemistry of Three-component White Dwarfs and Neutron Star Crusts: Phase Stability, Phase Stratification, and Physical Properties

NASA Astrophysics Data System (ADS)

Engstrom, T. A.; Yoder, N. C.; Crespi, V. H.

2016-02-01

A systematic search for multicomponent crystal structures is carried out for five different ternary systems of nuclei in a polarizable background of electrons, representative of accreted neutron star crusts and some white dwarfs. Candidate structures are “bred” by a genetic algorithm and optimized at constant pressure under the assumption of linear response (Thomas-Fermi) charge screening. Subsequent phase equilibria calculations reveal eight distinct crystal structures in the T = 0 bulk phase diagrams, five of which are complicated multinary structures not previously predicted in the context of compact object astrophysics. Frequent instances of geometrically similar but compositionally distinct phases give insight into structural preferences of systems with pairwise Yukawa interactions, including and extending to the regime of low-density colloidal suspensions made in a laboratory. As an application of these main results, we self-consistently couple the phase stability problem to the equations for a self-gravitating, hydrostatically stable white dwarf, with fixed overall composition. To our knowledge, this is the first attempt to incorporate complex multinary phases into the equilibrium phase-layering diagram and mass-radius-composition dependence, both of which are reported for He-C-O and C-O-Ne white dwarfs. Finite thickness interfacial phases (“interphases”) show up at the boundaries between single-component body-centered cubic (bcc) crystalline regions, some of which have lower lattice symmetry than cubic. A second application—quasi-static settling of heavy nuclei in white dwarfs—builds on our equilibrium phase-layering method. Tests of this nonequilibrium method reveal extra phases that play the role of transient host phases for the settling species.

Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof.

PubMed

Shao, Hua; Pinnavaia, Thomas J

2010-09-01

The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.

Effect of SiO2/B2O3 Ratio on the Crystallization Behavior and Dielectric Properties of Barium Strontium Titanate Glass-Ceramics Prepared by Sol-Gel Process

NASA Astrophysics Data System (ADS)

Chen, Yongzhou; Zhang, Yong; Song, Xiaozhen; Shen, Ziqin; Zhang, Tianyuan

2018-05-01

Ferroelectric glass-ceramics, with a basic composition 90 wt.% (Ba0.65Sr0.35)TiO3-10 wt.% (B2O3-nSiO2) (n = 0.5, 1, 3, 5) were synthesized by the sol-gel method and their phase development and dielectric properties were investigated by differential thermal analysis, x-ray diffraction, field emission scanning electron microscopy, dielectric temperature curves and impedance spectroscopy. From the differential thermal analysis, glass transition and crystallization behavior can be observed. From the x-ray diffraction study, two crystalline phases (Ba,Sr)TiO3 and Ba2TiSi2O8 were formed over the entire composition range of the glass-ceramics. In addition, the main crystal phase has undergone a transformation from (Ba,Sr)TiO3 to Ba2TiSi2O8 with the increase of n. A typical structure in which the crystal phase was surrounded by a glassy matrix has been observed in the scanning electron microscope images. As a result of temperature dependent dielectric property measurements, the dielectric constant increased obviously with the increase of n from 0.5 to 1. Further increasing n led to a reduction of the dielectric constant, which is in coincidence with the variation of the intensity of (Ba,Sr)TiO3 phase with n. According to the impedance spectroscopy analysis and the activation energy calculation, the relaxation peak in both Z″ and M″ data should be attributed to the crystal-glass interface, and the change of conduction mechanism with the increase of SiO2/B2O3 ratio may be attributed to the corresponding transition of the main crystal phase.

Separation of non-racemic mixtures of enantiomers: an essential part of optical resolution.

PubMed

Faigl, Ferenc; Fogassy, Elemér; Nógrádi, Mihály; Pálovics, Emese; Schindler, József

2010-03-07

Non-racemic enantiomeric mixtures form homochiral and heterochiral aggregates in melt or suspension, during adsorption or recrystallization, and these diastereomeric associations determine the distribution of the enantiomers between the solid and other (liquid or vapour) phases. That distribution depends on the stability order of the homo- and heterochiral aggregates (conglomerate or racemate formation). Therefore, there is a correlation between the binary melting point phase diagrams and the experimental ee(I)vs. ee(0) curves (ee(I) refers to the crystallized enantiomeric mixtures, ee(0) is the composition of the starting ones). Accordingly, distribution of the enantiomeric mixtures between two phases is characteristic and usually significant enrichment can be achieved. There are two exceptions: no enrichment could be observed under thermodynamically controlled conditions when the starting enantiomer composition corresponded to the eutectic composition, or when the method used was unsuitable for separation. In several cases, when kinetic control governed the crystallization, the character of the ee(0)-ee(I) curve did not correlate with the melting point binary phase diagram.

Synthesis of Self-Bonded Pellets of ETS-4 Phase by New Methodology of Preparation

NASA Astrophysics Data System (ADS)

De Luca, P.; Mastroianni, C.; Nagy, J. B.

2018-06-01

We hereby present the results of a research in order to prepare self-bonded pellets of ETS-4 phase by a new methodology of preparation. In particular, the pellets were prepared by kneading crystals of ETS-4 phase and a dry gel, the latter being the precursor for the synthesis of the ETS-4 phase crystals. One of the innovative aspects that is proposed and highlighted in this work is represented by the fact that the dry-gel acts as a “binder”. It is characterized by the same chemical composition of crystals, thus avoiding contamination with other elements. In addition, dry-gel allows, the promotion of nucleation phenomena and thus the formation of new crystals of ETS-4 during the pellets baking phases. The pellets were characterized by X-ray diffraction (XRD), Electron microscopy (SEM) and mechanical strength by hardness tester.

Biologically controlled minerals as potential indicators of life

NASA Technical Reports Server (NTRS)

Schwartz, D. E.; Mancinelli, R. L.; Kaneshiro, E.

1991-01-01

Minerals can be produced and deposited either by abiotic or biologic means. Regardless of their origin, mineral crystals reflect the environment conditions (e.g., temperature, pressure, chemical composition, and redox potential) present during crystal formation. Biologically-produced mineral crystals are grown or reworked under the control of their host organism and reflect an environment different from the abiotic environment. In addition, minerals of either biologic or abiotic origin have great longevities. For these reasons, biologically produced minerals have been proposed as biomarkers. Biomarkers are key morphological, chemical, and isotopic signatures of living systems that can be used to determine if life processes have occurred. Studies of biologically controlled minerals produced by the protist, Paramecium tetraurelia, were initiated since techniques have already been developed to culture them and isolate their crystalline material, and methods are already in place to analyze this material. Two direct crystalline phases were identified. One phase, whose chemical composition is high in Mg, was identified as struvite. The second phase, whose chemical composition is high in Ca, has not been previously found occurring naturally and may be considered a newly discovered material. Analyses are underway to determine the characteristics of these minerals in order to compare them with characteristics of these minerals in order to compare them with characteristics of minerals formed abiotically, but with the same chemical composition.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

High temperature crystalline superconductors from crystallized glasses

DOEpatents

Shi, Donglu

1992-01-01

A method of preparing a high temperature superconductor from an amorphous phase. The method involves preparing a starting material of a composition of Bi.sub.2 Sr.sub.2 Ca.sub.3 Cu.sub.4 Ox or Bi.sub.2 Sr.sub.2 Ca.sub.4 Cu.sub.5 Ox, forming an amorphous phase of the composition and heat treating the amorphous phase for particular time and temperature ranges to achieve a single phase high temperature superconductor.

Segregation of liquid crystal mixtures in topological defects

DOE PAGES

Rahimi, Mohammad; Ramezani-Dakhel, Hadi; Zhang, Rui; ...

2017-04-28

The structure and physical properties of liquid crystal (LC) mixtures are a function of composition, and small changes can have pronounced effects on observables, such as phase-transition temperatures. Traditionally, LC mixtures have been assumed to be compositionally homogenous. The results of chemically detailed simulations presented here show that this is not the case; pronounced deviations of the local order from that observed in the bulk at defects and interfaces lead to significant compositional segregation effects. More specifically, two disclination lines are stabilized in this work by introducing into a nematic liquid crystal mixture a cylindrical body that exhibits perpendicular anchoring.more » Here, it is found that the local composition deviates considerably from that of the bulk at the interface with the cylinder and in the defects, thereby suggesting new assembly and synthetic strategies that may capitalize on the unusual molecular environment provided by liquid crystal mixtures.« less

Miscibility, Crystallization, and Rheological Behavior of Solution Casting Poly(3-hydroxybutyrate)/poly(ethylene succinate) Blends Probed by Differential Scanning Calorimetry, Rheology, and Optical Microscope Techniques

NASA Astrophysics Data System (ADS)

Sun, Wei-hua; Qiao, Xiao-ping; Cao, Qi-kun; Liu, Jie-ping

2010-02-01

The miscibility and crystallization of solution casting biodegradable poly(3-hydroxybutyrate)/poly(ethylene succinate) (PHB/PES) blends was investigated by differential scanning calorimetry, rheology, and optical microscopy. The blends showed two glass transition temperatures and a depression of melting temperature of PHB with compositions in phase diagram, which indicated that the blend was partially miscible. The morphology observation supported this result. It was found that the PHB and PES can crystallize simultaneously or upon stepwise depending on the crystallization temperatures and compositions. The spherulite growth rate of PHB increased with increasing of PES content. The influence of compositions on the spherulitic growth rate for the partially miscible polymer blends was discussed.

Phase separation, crystallization and polyamorphism in the Y2O3 Al2O3 system

NASA Astrophysics Data System (ADS)

Skinner, Lawrie B.; Barnes, Adrian C.; Salmon, Philip S.; Crichton, Wilson A.

2008-05-01

A detailed study of glass formation from aerodynamically levitated liquids in the (Y2O3)x(Al2O3)1-x system for the composition range 0.21<=x<=0.41 was undertaken by using pyrometric, optical imaging and x-ray diffraction methods. Homogeneous and clear single-phase glasses were produced over the composition range 0.27 \\lesssim x \\lesssim 0.33 . For Y2O3-rich compositions (0.33 \\lesssim x \\le 0.375 ), cloudy materials were produced which contain inclusions of crystalline yttrium aluminium garnet (YAG) of diameter up to 40 µm in a glassy matrix. For Y2O3-poor compositions around x = 0.24, cloudy materials were also produced, but it was not possible to deduce whether this resulted from (i) sub-micron inclusions of a nano-crystalline or glassy material in a glassy matrix or (ii) a glass formed by spinodal decomposition. For x = 0.21, however, the sample cloudiness results from crystallization into at least two phases comprising yttrium aluminium perovskite and alumina. The associated pyrometric cooling curve shows slow recalescence events with a continuous and slow evolution of excess heat which contrasts with the sharp recalescence events observed for the crystallization of YAG at compositions near x = 0.375. The materials that are the most likely candidates for demonstrating homogeneous nucleation of a second liquid phase occur around x = 0.25, which corresponds to the limit for formation of a continuous random network of corner-shared AlO4 tetrahedra.

Development of a Single-Crystal Fifth-Generation Nickel Superalloy

NASA Astrophysics Data System (ADS)

Petrushin, N. V.; Elyutin, E. S.; Visik, E. M.; Golynets, S. A.

2017-11-01

The chemical and phase compositions of a rhenium-ruthenium-containing fifth-generation VZhM8 nickel superalloy, which is intended for single-crystal turbine blades of an aviation engine, are calculated using computer simulation. VZhM8 alloy <001>, <011>, and <111> single crystals are fabricated. The microstructure, the γ/γ' misfit, the segregation coefficients of alloying elements, the dissolution temperature of the γ' phase, and the solidus and liquidus temperatures of the VZhM8 alloy single crystals in the as-cast state and after heat treatment are studied. The temperature-time dependences of the static elastic modulus, the short-term mechanical properties, and the long-term strength of the alloy single crystals are determined

Phase coexistence and domain configuration in Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-0.34PbTiO{sub 3} single crystal revealed by synchrotron-based X-ray diffractive three-dimensional reciprocal space mapping and piezoresponse force microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Ruixue; Yang, Bin, E-mail: binyang@hit.edu.cn; Sun, Enwei

The crystalline phases and domain configuration in the morphotropic phase boundary composition Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-0.34PbTiO{sub 3} (PMN-0.34PT) single crystal have been investigated by synchrotron-based X-ray 3D Reciprocal Space Mapping (3D-RSM) and Piezoresponse Force Microscopy. The coexistence of tetragonal (T) and monoclinic M{sub C} phases in this PMN-0.34PT single crystal is confirmed. The affiliation of each diffraction spot in the 3D-RSM was identified with the assistance of qualitative simulation. Most importantly, the twinning structure between different domains in such a mixed phase PMN-PT crystal is firmly clarified, and the spatial distribution of different twin domains is demonstrated. In addition, themore » lattice parameters of T and M{sub C} phases in PMN-0.34PT single crystal as well as the tilting angles of crystal lattices caused by the interfacial lattice mismatch are determined.« less

Primary Phase Field of the Pb-Doped 2223 High-Tc Superconductor in the (Bi, Pb)-Sr-Ca-Cu-O System

PubMed Central

Wong-Ng, W.; Cook, L. P.; Kearsley, A.; Greenwood, W.

1999-01-01

Both liquidus and subsolidus phase equilibrium data are of central importance for applications of high temperature superconductors in the (Bi, Pb)-Sr-Ca-Cu-O system, including material synthesis, melt processing and single crystal growth. The subsolidus equilibria of the 110 K high-Tc Pb-doped 2223 ([Bi, Pb], Sr, Ca, Cu) phase and the location of the primary phase field (crystallization field) have been determined in this study. For the quantitative determination of liquidus data, a wicking technique was developed to capture the melt for quantitative microchemical analysis. A total of 29 five-phase volumes that include the 2223 phase as a component was obtained. The initial melt compositions of these volumes range from a mole fraction of 7.3 % to 28.0 % for Bi, 11.3 % to 27.8 % for Sr, 1.2 % to 19.4 % for Pb, 9.8 % to 30.8 % for Ca, and 17.1 % to 47.0 % for Cu. Based on these data, the crystallization field for the 2223 phase was constructed using the convex hull technique. A section of this “volume” was obtained by holding two components of the composition at the median value, allowing projection on the other three axes to show the extent of the field.

Crystallization of spray-dried lactose/protein mixtures in humid air

NASA Astrophysics Data System (ADS)

Shawqi Barham, A.; Kamrul Haque, Md.; Roos, Yrjö H.; Kieran Hodnett, B.

2006-10-01

An in situ crystallization technique with X-ray diffraction analysis complemented by ex situ scanning electron microscopy and chromatographic analysis of the α/( α+ β) solid-state anomeric ratios has been developed to study the crystallization of lactose/protein mixtures in humid air. This technique was used to determine changes in phase composition and morphology during crystallization. Following an induction period during which water is sorbed, crystallization is rapid and the predominant phase observed using the in situ method in spray-dried lactose/sodium-caseinate, albumin and gelatin is α-lactose monohydrate. However, in the case of spray-dried lactose/whey protein isolate (WPI) the predominant phase that appears is the α/ β mixed phase with smaller amounts of α-lactose monohydrate. With pure lactose the α/ β mixed phase appears as a transient shortly after the onset of crystallization and α-lactose monohydrate and β-lactose both appear as stable crystalline phases at longer times. Another transient phase with 2 θ=12.2°, 20.7° and 21.8° was observed in spray-dried lactose/albumin. This phase decomposed as α-lactose monohydrate developed. Three phases seem to persist in the case of spray-dried lactose/gelatin, namely the phase with peaks at 2 θ=12.2°, 20.7° and 21.8°, α-lactose monohydrate and β-lactose for the duration of the in situ experiment.

The Phase Transformation and Crystal Structure Studies of Strontium Substituted Barium Monoferrite

NASA Astrophysics Data System (ADS)

Mulyawan, A.; Adi, W. A.; Mustofa, S.; Fisli, A.

2017-03-01

Unlike other AFe2O4 ferrite materials, Barium Monoferrite (BaFe2O4) have an orthorhombic structure which is very interesting to further study the crystal structure and phase formation. In this study, Strontium substituted Barium Monoferrite in the form of Ba(1-x)Sr(x)Fe2O4 has successfully been synthesized through solid state reaction method which includes BaCO3, SrCO3, and Fe2O3 as starting materials. Ba(1-x)Sr(x)Fe2O4 was made by varying the dopant composition of Strontium (Sr2+) from x = 0, 0.1, 0.3, and 0.5. Each composition was assisted by ethanol and continued to the milling process for 5 hours then followed by sintering process at 900 °C for 5 hours. The phase transformation was studied by using X-ray diffractometer (XRD) and Rietveld refinement using General Structure Analysis System (GSAS) also 3D crystal visualization using VESTA. Referring to the refinement results, a single phase of BaFe2O4 was formed in x = 0 and 0.1. The composition has orthorhombic structure, space group B b21m, and lattice parameters of a = 19.0229, b = 5.3814 c = 8.4524 Å, α = β = γ = 90° and a = 18.9978, b = 5.3802 c = 8.4385 Å, α = β = γ = 90° respectively. In the composition of x = 0.3 it was found that the phase of BaSrFe4O8 begin to form due to the overload expansion of the Sr2+ occupancy which made the distortion of the initial lattice parameters and finally in the x = 0.5 composition the single phase of BaSrFe4O8 was clearly formed. Energy Dispersive Spectroscopy (EDS) was used to confirm the change of the material structure by measuring the elemental compound composition ratio. The result of EDS spectra clearly exhibited the dominant elements were Barium (Ba), Strontium (Sr), Iron (Fe), and Oxygen (O) with the compound ratio (Atomic percentage and mass percentage) correspond to the BaFe2O4 and BaSrFe4O8 phase.

Timescale of Petrogenetic Processes Recorded in the Mount Perkins Magma System, Northern Colorado River Extension Corridor, Arizona

NASA Technical Reports Server (NTRS)

Danielson, Lisa R.; Metcalf, Rodney V.; Miller, Calvin F.; Rhodes Gregory T.; Wooden, J. L.

2013-01-01

The Miocene Mt. Perkins Pluton is a small composite intrusive body emplaced in the shallow crust as four separate phases during the earliest stages of crustal extension. Phase 1 (oldest) consists of isotropic hornblende gabbro and a layered cumulate sequence. Phase 2 consists of quartz monzonite to quartz monzodiorite hosting mafic microgranitoid enclaves. Phase 3 is composed of quartz monzonite and is subdivided into mafic enclave-rich zones and enclave-free zones. Phase 4 consists of aphanitic dikes of mafic, intermediate and felsic compositions hosting mafic enclaves. Phases 2-4 enclaves record significant isotopic disequilibrium with surrounding granitoid host rocks, but collectively enclaves and host rocks form a cogenetic suite exhibiting systematic variations in Nd-Sr-Pb isotopes that correlate with major and trace elements. Phases 2-4 record multiple episodes of magma mingling among cogenetic hybrid magmas that formed via magma mixing and fractional crystallization at a deeper crustal. The mafic end-member was alkali basalt similar to nearby 6-4 Ma basalt with enriched OIB-like trace elements and Nd-Sr-Pb isotopes. The felsic end-member was a subalkaline crustal-derived magma. Phase 1 isotropic gabbro exhibits elemental and isotopic compositional variations at relatively constant SiO2, suggesting generation of isotropic gabbro by an open-system process involving two mafic end-members. One end-member is similar in composition to the OIB-like mafic end-member for phases 2-4; the second is similar to nearby 11-8 Ma tholeiite basalt exhibiting low epsilon (sub Nd), and depleted incompatible trace elements. Phase 1 cumulates record in situ fractional crystallization of an OIB-like mafic magma with isotopic evidence of crustal contamination by partial melts generated in adjacent Proterozoic gneiss. The Mt Perkins pluton records a complex history in a lithospheric scale magma system involving two distinct mantle-derived mafic magmas and felsic magma sourced in the crust. Mixing and fractional crystallization of these magmas at various levels in the crust generated a suite of intermediate composition magmas. U-Pb zircon SHRIMP ages of phase 1 (15.7 +/- 0.2 Ma), phase 3 (15.8 +/- 0.2 Ma) and phase 4 (15.4 +/- 0.3 Ma) document a 100-300k year timescale for petrogenetic processes recorded in the Mt Perkins magma system.

Origin of Aphyric Phonolitic Magmas: Natural Evidences and Experimental Constraints

NASA Astrophysics Data System (ADS)

Masotta, M.; Freda, C.; Gaeta, M.

2010-12-01

Large explosive phonolitic eruptions are commonly characterised by aphyric juvenile eruptive products. Taking into account the low density contrast among phonolitic composition and settling phases (i.e., feldspar and leucite), the almost complete lack of crystals in these differentiated compositions rises the question of which process could produce such an efficient crystal-melt separation. Seeking for an answer, we have investigated crystallization in presence of a thermal gradient as a possible mechanism for crystal-melt separation, considering both chemical and physical effects acting on a variably crystallized system. Using a natural tephri-phonolitic composition as starting material (M.te Aguzzo scoria cone, Sabatini Volcanic District, Central Italy), we have reproduced thermal gradient-driven crystallization in order to simulate the crystallization process in a thermally zoned magma chamber. Crystallization degree (paragenesis made of clinopyroxene±feldspars±leucite) as well as melt composition varies along the thermal gradient. In particular, melt composition ranges from the tephri-phonolitic starting composition at the bottom of the charge (hottest and aphyric zone) to phonolitic at the top (cooler and heterogeneously-crystallised zone). Backscattered images of experimental products clearly evidence: i) the aphyric tephri-phonolitic melt region at the bottom of the charge; ii) a drop-shaped crystal clustering in the middle zone; and iii) large aphyric belt and pockets (up to 100 µm wide) of phonolitic melt, with large deformed-shaped sanidine occurring at their margin, at the charge top region. The latter two features, resulting from solid-melt displacements, suggest that the segregation of phonolitic melt can be related to crystal sinking and compaction. On the other hand, the compositional variability of the melt along the thermal gradient is directly related to the crystallization degree, indicating that chemical diffusion and thermal migration have negligible effect at the experimental scale. Experimental results suggest that, in presence of a thermal gradient, a filter-press differentiation mechanism (i.e. sinking+compaction) is able to produce heterogeneous magma differentiation characterised by a wide range of melt compositions (in our case from tephri-phonolitic to phonolitic). Although the limitation due to the vertical shape of the charge and consequent shear effects occurring at the lateral walls (thus limiting the mobility of the crystal clusters), experimental duration of 24 h is enough to allow crystal-melt separation by means of settling and compaction, indicating that timescale for such a process is extremely rapid and effective at experimental conditions. Actually, experimental textures and phase relations are in good agreement with those observed in natural lithic enclaves (from Sabatini Volcanic District) representative of the crystallizing boundary layer of a phonolitic magma chamber. Thus, we speculate that gravitative collapses of a mushy zone from the magma chamber roof of a thermally zoned magma chamber may produce top accumulation of highly differentiated and aphyric melts.

Investigation of Interrelation between Deformation, Composition and Structural Characteristics of Magnesium Oxychloride Cements

NASA Astrophysics Data System (ADS)

Averina, G. F.; Chernykh, T. N.; Kramar, L. Ya

2017-11-01

The paper studies the process of volume deformation changes in magnesium cement at its hardening in accordance with its composition and structural peculiarities, which result from the roasting parameters of the raw materials. The study has been carried out with the aim of broadening raw materials sources for production of magnesia cements and construction materials through the use waste products of ore-dressing and processing enterprises. The mineralogical and phase composition of magnesium cements, obtained on the basis of magnesite with high content of impurity minerals from the mine dumps, has been studied by the X-ray phase analysis and derivatography. The roasting of the initial raw materials was carried out at various temperature conditions in order to get cements of different activities. The typical content of hydrated phases has been found for the hardened magnesian stone obtained from cements with different activity degrees. The characteristics of volume deformations developed in the magnesian stone have been described in relation to its phase composition. The influence of low- and high-activity crystals and calcium oxide crystals on the soundness and the structural integrity of magnesian stone has been covered.

Dielectric properties and phase transition behaviors in (1-x)PbZrO3-xPb(Mg1/2W1/2)O3 ceramics

NASA Astrophysics Data System (ADS)

Vittayakorn, Naratip; Charoonsuk, Piyanut; Kasiansin, Panisara; Wirunchit, Supamas; Boonchom, Banjong

2009-09-01

The solid solution of lead zirconate [PbZrO3 (PZ)] and lead magnesium tungstate [Pb(Mg1/2W1/2)O3 (PMW)] has been synthesized by the wolframite precursor method. The crystal structure, phase transformations, dielectric and thermal properties of (1-x)PZ-xPMW, where x =0.00-0.10, were investigated. The crystal structure of sintered ceramics was analyzed by x-ray diffraction. Phase-pure perovskite was obtained for all compositions. Furthermore, a change from orthorhombic to rhombohedral symmetry was observed as the mole fraction of increased PMW. As a result, it was found that PbZrO3-Pb(Mg1/2W1/2)O3 undergoes successive transitions from the antiferroelectric phase to the ferroelectric phase to the paraelectric state. The coexistence of orthorhombic and rhombohedral phases in this binary system is located near the composition x =0.1.

Interfacial free energy controlling glass-forming ability of Cu-Zr alloys.

PubMed

Kang, Dong-Hee; Zhang, Hao; Yoo, Hanbyeol; Lee, Hyun Hwi; Lee, Sooheyong; Lee, Geun Woo; Lou, Hongbo; Wang, Xiaodong; Cao, Qingping; Zhang, Dongxian; Jiang, Jianzhong

2014-06-04

Glass is a freezing phase of a deeply supercooled liquid. Despite its simple definition, the origin of glass forming ability (GFA) is still ambiguous, even for binary Cu-Zr alloys. Here, we directly study the stability of the supercooled Cu-Zr liquids where we find that Cu64Zr36 at a supercooled temperature shows deeper undercoolability and longer persistence than other neighbouring compositions with an equivalent driving Gibbs free energy. This observation implies that the GFA of the Cu-Zr alloys is significantly affected by crystal-liquid interfacial free energy. In particular, the crystal-liquid interfacial free energy of Cu64Zr36 in our measurement was higher than that of other neighbouring liquids and, coincidently a molecular dynamics simulation reveals a larger glass-glass interfacial energy value at this composition, which reflects more distinct configuration difference between liquid and crystal phase. The present results demonstrate that the higher crystal-liquid interfacial free energy is a prerequisite of good GFA of the Cu-Zr alloys.

Reinforcement effect of poly(butylene succinate) (PBS)-grafted cellulose nanocrystal on toughened PBS/polylactic acid blends.

PubMed

Zhang, Xuzhen; Zhang, Yong

2016-04-20

Poly(butylene succinate) (PBS)/polylactic acid (PLA) blends modified with dicumyl peroxide (DCP) were reinforced by PBS-g-cellulose nanocrystal (CNC) through melt mixing. PBS-g-CNC was prepared through in situ polymerization and its structure was confirmed by FTIR, (13)C NMR, XPS and GPC analysis after saponification. The morphological analysis of PBS/PLA/PBS-g-CNC composites before and after etched by CH2Cl2 shows that the addition of DCP and PBS-g-CNC could decrease the size of PBS as a dispersed phase in PLA matrix and improve the dispersion of PBS-g-CNC in both PBS and PLA phases, which could affect the crystallization and mechanical properties of composites. The crystallinity of PLA α'-phase crystal in PBS/PLA/PBS-g-CNC composites is increased obviously by the addition of PBS-g-CNC, leading to an increase of the crystallinity of the composites. PBS/PLA blends modified by DCP have high Notched Izod impact strength and moduli, and the values are increased by the addition of PBS-g-CNC. Both storage modulus and glass translation temperature of PBS/PLA blend are increased by DCP and PBS-g-CNC, which is proved by DMA results, showing a weak molecular segment mobility of PBS/PLA matrix. The addition of DCP decreases the crystallization temperature and crystallinity of PBS/PLA composite, but increases the thermal stability of composites, mostly because of the crosslink effect of DCP on PBS/PLA matrix. Copyright © 2015 Elsevier Ltd. All rights reserved.

Crystallization Kinetics of a Solid Oxide Fuel Cell Seal Glass by Differential Thermal Analysis

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Gamble, Eleanor A.

2005-01-01

Crystallization kinetics of a barium calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells, have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder x-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO3 and hexacelsian (BaAl2Si2O8) were the primary crystalline phases whereas monoclinic celsian (BaAl2Si2O8) and (Ba(x), Ca(y))SiO4 were also detected as minor phases. Needle-shaped BaSiO3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long term heat treatments at 750 to 900 C.

Crystal growth of argyrodite-type phases Cu 8-xGeS 6-xI x and Cu 8-xGeSe 6-xI x (0⩽ x⩽0.8)

NASA Astrophysics Data System (ADS)

Tomm, Yvonne; Schorr, Susan; Fiechter, Sebastian

2008-04-01

The growth of single crystalline argyrodites of type Cu 8-xGeX 6-xY x ( X=S, Se; Y=I) is reported. These materials undergo solid-solid phase transitions at temperatures ranging from 30 to 90 °C. In the high temperature phase, Cu 8GeS 6 crystallizes in the cubic space group F4¯3m. In the low temperature phase, the compound is present in the orthorhombic space group Pmn2 1. Cu 8GeSe 6 appears exclusively in the hexagonal space groups P6 3mc or P6 3cm, respectively. Single crystals of these argyrodites were obtained by chemical vapor transport in a temperature gradient Δ T=980-950 and Δ T=700-620 °C for sulfides and selenides, respectively. As a result of the growth process, the high temperature phase remains stable even at ambient temperature by incorporation of the transport agent iodine during the growth process. As determined by energy dispersive X-ray analysis (EDAX), the composition of the sulfide crystals grown ranges from Cu 8GeS 6 to Cu 7.16GeS 5.16I 0.84. The selenide crystallizes as Cu 7.69GeSe 5.69I 0.31. In contrast, the solid state reaction of the elements Cu, Ge and X produces a material in the low temperature modification with an ideal composition of Cu 8GeX 6.

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.; Drummond, Charles H., III

1991-01-01

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glass transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder X ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structural transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Crystallization and properties of Sr-Ba aluminosilicate glass-ceramic matrices

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.; Drummond, Charles H., III

1991-01-01

Powders of roller quenched (Sr,Ba)O-Al2O3-2SiO2 glasses of various compositions were uniaxially pressed into bars and hot isostatically pressed at 1350 C for 4 hours or cold isostatically pressed and sintered at different temperatures between 800 to 1500 C for 10 or 20 hours. Densities, flexural strengths, and linear thermal expansion were measured for three compositions. The glasss transition and crystallization temperatures were determined by Differential Scanning Calorimetry (DSC). The liquidus and crystallization temperature from the melt were measured using high temperature Differential Thermal Analysis (DTA). Crystalline phases formed on heat treatment of the glasses were identified by powder x ray diffraction. In Sr containing glasses, the monoclinic celsian phase always crystallized at temperatures above 1000 C. At lower temperatures, the hexagonal analog formed. The temperature for orthorhombic to hexagonal structure transformation increased monotonically with SrO content, from 327 C for BaO-Al2O3-2SiO2 to 758 C for SrO-Al2O3-2SiO2. These glass powders can be sintered to almost full densities and monoclinic celsian phase at a relatively low temperature of 1100 C.

Increasing dissolution of trospium chloride by co-crystallization with urea

NASA Astrophysics Data System (ADS)

Skořepová, Eliška; Hušák, Michal; Čejka, Jan; Zámostný, Petr; Kratochvíl, Bohumil

2014-08-01

The search for various solid forms of an active pharmaceutical ingredient (API) is an important step in drug development. Our aim was to prepare co-crystals of trospium chloride, an anticholinergic drug used for the treatment of incontinence, and to investigate if they have advantageous properties for drug formulation. Phase identification was done by powder X-ray diffraction and single-crystal X-ray diffraction. The chemical composition was verified by solution NMR and the dissolution rate of the prepared phases was studied by IDR (intrinsic dissolution rate). For further analysis of phase stability and transitions, combined thermal analysis and temperature-resolved X-ray powder diffraction were used. Urea was selected as a co-crystallization partner. Trospium chloride urea (1:1) co-crystal was prepared by a solvent evaporation. From single-crystal data, the co-crystal structure was solved in a space group P21/c and compared to previously published structures of trospium chloride. Intrinsic dissolution rate revealed that the co-crystal dissolves 32% faster than pure API. However, its low thermal and pressure stability makes it a challenging choice for the final drug formulation.

Bidirectional phase-modulated hybrid cable television/radio-over-fiber lightwave transport systems.

PubMed

Chen, Chia-Yi; Wu, Po-Yi; Lu, Hai-Han; Lin, Ying-Pyng; Gao, Ming-Cian; Wen, Jian-Ying; Chen, Hwan-Wen

2013-02-15

A bidirectional phase-modulated hybrid cable television/radio-over-fiber lightwave transport system employing fiber Bragg grating tilt filter as a phase modulation-to-intensity modulation conversion scheme is proposed and demonstrated. Impressive performances of carrier-to-noise ratio, composite second-order, composite triple-beat, and bit-error rate are obtained in our proposed systems over a combination of 40 km single-mode fiber-and 1.43 km photonic crystal fiber transmission.

In vitro bioactivity of a biocomposite fabricated from HA and Ti powders by powder metallurgy method.

PubMed

Ning, C Q; Zhou, Y

2002-07-01

Traditionally, hydroxyapatite was used as a coating material on titanium substrate by various techniques. In the present work, a biocomposite was successfully fabricated from hydroxyapatite and titanium powders by powder metallurgy method. Bioactivity of the composite in a simulated body fluid (SBF) was investigated. Main crystal phases of the as-fabricated composite are found to be Ti2O, CaTiO3, CaO, alpha-Ti and a TiP-like phase. When the composite is immersed in the simulated body fluid for a certain time, a poor-crystallized, calcium-deficient, carbonate-containing apatite film will form on the surface of the composite. The time required to induce apatite nucleation is within 2 h. In addition, the apatite is also incorporated with a little magnesium and chlorine element. It is found that Ti2O has the ability to induce the formation of bone-like apatite in the SBF. And a dissolve of the CaO phase could also provide favorable conditions for the apatite formation, by forming open pores on the surface of the composite and increasing the degree of supersaturation of the SBF with respect to the apatite.

Phase Behavior of Pyrene and Vinyl Polymers with Aromatic Side Groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kangovi, Gagan N.; Lee, Sangwoo

The phase behavior and thermodynamic properties of mixtures of pyrene and model vinyl polymers with and without aromatic side groups are investigated using differential scanning calorimetry (DSC) measurements. The melting temperature and associated heat of melting of the pyrene crystals in the mixtures are utilized to extract the effective interaction parameters χ and the composition of polymer-rich phases, respectively. The χ of pyrene mixed with polymers with aromatic side groups investigated in this study, polystyrene, poly(2-vinylpyridine), and poly(3-vinylanisole), is less than 0.5 at the melting point of the pyrene crystals, suggesting that pyrene and the polymers with aromatic sides groupsmore » are enthalpically compatible, likely due to aromatic π–π interactions. In contrast, the χ of pyrene mixed with poly(1,4-isoprene) or poly(ethylene-alt-propylene) is larger than 0.5. The DSC measurements also enable characterization of the composition of polymer-rich phases. Interestingly, the polymers with aromatic side groups are found to have more pronounced miscibility with pyrene at symmetric compositions.« less

Evaluation of stability region for scandium-containing rare-earth garnet single crystals and their congruent-melting compositions

NASA Astrophysics Data System (ADS)

Kaurova, I. A.; Domoroshchina, E. N.; Kuz'micheva, G. M.; Rybakov, V. B.

2017-06-01

Single crystals of scandium-containing rare-earth garnets in system R-Sc-C-O (R3+=Y, Gd; C3+=Al, Ga) have been grown by the Czochralski technique. X-ray diffraction analysis has been used to refine crystal compositions. The fundamental difference between the melt compositions and compositions of grown crystals has been found (except for compositions of congruent-melting compounds, CMC). The specific features of garnet solid solution formation have been established and the ternary diagrams with real or hypothetical phases have been built. The dinamics of coordination polyhedra changes with the formation of substitutional solid solutions have been proposed based on the mathematical modeling and experimental data. Possible existence of CMC with garnet structure in different systems as well as limit content of Sc ions in dodecahedral and octahedral sites prior to their partial substitution of ions, located in other sites, have been evaluated. It was established that the redistribution of cations over crystallographic sites (antistructural point defects) due to system self-organization to maintain its stability may be accompanied by cation ordering and the symmetry change of individual polyhedrons and/or the whole crystal.

Programming scale-free optics in disordered ferroelectrics.

PubMed

Parravicini, Jacopo; Conti, Claudio; Agranat, Aharon J; DelRe, Eugenio

2012-06-15

Using the history dependence of a dipolar glass hosted in a compositionally disordered lithium-enriched potassium tantalate niobate (KTN:Li) crystal, we demonstrate scale-free optical propagation at tunable temperatures. The operating equilibration temperature is determined by previous crystal spiralling in the temperature/cooling-rate phase space.

Crystallization history of lunar picritic basalt sample 12002 - Phase-equilibria and cooling-rate studies

NASA Technical Reports Server (NTRS)

Walker, D.; Kirkpatrick, R. J.; Longhi, J.; Hays, J. F.

1976-01-01

Experimental crystallization of a lunar picrite composition (sample 12002) at controlled linear cooling rates produces systematic changes in the temperature at which crystalline phases appear, in the texture, and in crystal morphology as a function of cooling rate. Phases crystallize in the order olivine, chromium spinel, pyroxene, plagioclase, and ilmenite during equilibrium crystallization, but ilmenite and plagioclase reverse their order of appearance and silica crystallizes in the groundmass during controlled cooling experiments. The partition of iron and magnesium between olivine and liquid is independent of cooling rate, temperature, and pressure. Comparison of the olivine nucleation densities in the lunar sample and in the experiments indicates that the sample began cooling at about 1 deg C/hr. Pyroxene size, chemistry, and growth instability spacings, as well as groundmass coarseness, all suggest that the cooling rate subsequently decreased by as much as a factor of 10 or more. The porphyritic texture of this sample, then, is produced at a decreasing, rather than a discontinuously increasing, cooling rate.

Phase Equilibria and Crystal Chemistry in Portions of the System SrO-CaO-Bi2O3-CuO, Part IV— The System CaO-Bi2O3-CuO

PubMed Central

Burton, B. P.; Rawn, C. J.; Roth, R. S.; Hwang, N. M.

1993-01-01

New data are presented on the phase equilibria and crystal chemistry of the binary systems CaO-Bi2O3 and CaO-CuO and the ternary CaO-Bi2O3-CuO. Symmetry data and unit cell dimensions based on single crystal and powder x-ray diffraction measurements are reported for several of the binary CaO-Bi2O3 phases, including corrected compositions for Ca4Bi6O13 and Ca2Bi2O5. The ternary system contains no new ternary phases which can be formed in air at ~700–900 °C. PMID:28053484

Structural phase transitions in the Ag{sub 2}Nb{sub 4}O{sub 11}-Na{sub 2}Nb{sub 4}O{sub 11} solid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodward, David I., E-mail: d.i.woodward@warwick.ac.uk; Lees, Martin R.; Thomas, Pam A.

2012-08-15

The phase transitions between various structural modifications of the natrotantite-structured system xAg{sub 2}Nb{sub 4}O{sub 11}-(1-x)Na{sub 2}Nb{sub 4}O{sub 11} have been investigated and a phase diagram constructed as a function of temperature and composition. This shows three separate phase transition types: (1) paraelectric-ferroelectric, (2) rhombohedral-monoclinic and (3) a phase transition within the ferroelectric rhombohedral zone between space groups R3c and R3. The parent structure for the entire series has space group R3{sup Macron }c. Compositions with x>0.75 are rhombohedral at all temperatures whereas compositions with x<0.75 are all monoclinic at room temperature and below. At x=0.75, rhombohedral and monoclinic phases coexistmore » with the phase boundary below room temperature being virtually temperature-independent. The ferroelectric phase boundary extends into the monoclinic phase field. No evidence was found for the R3-R3c phase boundary extending into the monoclinic phase field and it is concluded that a triple point is formed. - Graphical abstract: Phase diagram for xAg{sub 2}Nb{sub 4}O{sub 11}-(1-x)Na{sub 2}Nb{sub 4}O{sub 11} solid solution showing changes in crystal symmetry as a function of temperature and composition. The crystal structure is depicted. Highlights: Black-Right-Pointing-Triangle Ferroelectric, rhombohedral Ag{sub 2}Nb{sub 4}O{sub 11} in solid solution with monoclinic Na{sub 2}Nb{sub 4}O{sub 11}. Black-Right-Pointing-Triangle Three phase boundaries were studied as a function of composition and temperature. Black-Right-Pointing-Triangle Both rhombohedral and monoclinic variants exhibit ferroelectricity. The parent phase of the series has space group R3{sup Macron }c.« less

High speed X-ray phase contrast imaging of energetic composites under dynamic compression

NASA Astrophysics Data System (ADS)

Parab, Niranjan D.; Roberts, Zane A.; Harr, Michael H.; Mares, Jesus O.; Casey, Alex D.; Gunduz, I. Emre; Hudspeth, Matthew; Claus, Benjamin; Sun, Tao; Fezzaa, Kamel; Son, Steven F.; Chen, Weinong W.

2016-09-01

Fracture of crystals and frictional heating are associated with the formation of "hot spots" (localized heating) in energetic composites such as polymer bonded explosives (PBXs). Traditional high speed optical imaging methods cannot be used to study the dynamic sub-surface deformation and the fracture behavior of such materials due to their opaque nature. In this study, high speed synchrotron X-ray experiments are conducted to visualize the in situ deformation and the fracture mechanisms in PBXs composed of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and hydroxyl-terminated polybutadiene binder doped with iron (III) oxide. A modified Kolsky bar apparatus was used to apply controlled dynamic compression on the PBX specimens, and a high speed synchrotron X-ray phase contrast imaging (PCI) setup was used to record the in situ deformation and failure in the specimens. The experiments show that synchrotron X-ray PCI provides a sufficient contrast between the HMX crystals and the doped binder, even at ultrafast recording rates. Under dynamic compression, most of the cracking in the crystals was observed to be due to the tensile stress generated by the diametral compression applied from the contacts between the crystals. Tensile stress driven cracking was also observed for some of the crystals due to the transverse deformation of the binder and superior bonding between the crystal and the binder. The obtained results are vital to develop improved understanding and to validate the macroscopic and mesoscopic numerical models for energetic composites so that eventually hot spot formation can be predicted.

High speed X-ray phase contrast imaging of energetic composites under dynamic compression

DOE PAGES

Parab, Niranjan D.; Roberts, Zane A.; Harr, Michael H.; ...

2016-09-26

Fracture of crystals and subsequent frictional heating are associated with formation of hot spots in energetic composites such as polymer bonded explosives (PBXs). Traditional high speed optical imaging methods cannot be used to study the dynamic sub-surface deformation and fracture behavior of such materials due to their opaque nature. In this study, high speed synchrotron X-ray experiments are conducted to visualize the in situ deformation and fracture mechanisms in PBXs manufactured using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and hydroxyl-terminated polybutadiene (HTPB) binder. A modified Kolsky bar apparatus was used to apply controlled dynamic compression on the PBX specimens, and a high speedmore » synchrotron X-ray phase contrast imaging (PCI) setup was used to record the in situ deformation and failure in the specimens. The experiments show that synchrotron X-ray PCI provides a sufficient contrast between the HMX crystals and the doped binder, even at ultrafast recording rates. Under dynamic compression, most of the cracking in the crystals was observed to be due to the tensile stress generated by the diametral compression applied from the contacts between the crystals. Tensile stress driven cracking was also observed for some of the crystals due to the transverse deformation of the binder and superior bonding between the crystal and the binder. In conclusion, the obtained results are vital to develop improved understanding and to validate the macroscopic and mesoscopic numerical models for energetic composites so that eventually hot spot formation can be predicted.« less

Effect of composition ratio on the thermal and physical properties of semicrystalline PLA/PHB-HHx composites.

PubMed

Lim, Jung Seop; Park, Ku-il; Chung, Gun Soo; Kim, Jong Hoon

2013-05-01

In this study, composites of semicrystalline, biodegradable polylactide (PLA) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-HHx) were prepared by direct melt compounding. The physical and thermal properties of the composites were investigated as a function of the composition ratio. Differential scanning calorimetry analysis indicated that PLA and PHB-HHx formed immiscible composites over the observed range of composition. The crystallization of PLA was gradually suppressed by increasing proportions of PHB-HHx. Dynamic mechanical analysis results confirmed that the innate ductility of PHB-HHX and its inhibiting effect on PLA crystallization improved the stiffness of the composite compared to those of neat PLA. The infrared spectra of the immiscible PLA/PHB-HHx composites at two crystallization temperatures (30 °C, 130 °C) were obtained and presented. At 30 °C, PHB-HHx existed as crystalline domains in the PLA matrix, while, amorphous phase of molten PHB-HHx was diffused within the crystalline phase of PLA at 130 °C. The interaction between PHB-HHX and PLA could not be elucidated from the temperature data. Mechanical tests showed that the addition of PHB-HHx improves ductility of PLA/PHB-HHx composite. Morphological analysis revealed that small proportions of PHB-HHx exhibited less tendency to aggregate, which resulted in greater plastic deformation and improved toughness. From this study, PLA blended with small portions of PHB-HHx may further expand the use of bio-friendly resources in a variety of applications such as flexible films, food packaging and something like that. Copyright © 2013 Elsevier B.V. All rights reserved.

Polymer composites and porous materials prepared by thermally induced phase separation and polymer-metal hybrid methods

NASA Astrophysics Data System (ADS)

Yoon, Joonsung

The primary objective of this research is to investigate the morphological and mechanical properties of composite materials and porous materials prepared by thermally induced phase separation. High melting crystallizable diluents were mixed with polymers so that the phase separation would be induced by the solidification of the diluents upon cooling. Theoretical phase diagrams were calculated using Flory-Huggins solution thermodynamics which show good agreement with the experimental results. Porous materials were prepared by the extraction of the crystallized diluents after cooling the mixtures (hexamethylbenzene/polyethylene and pyrene/polyethylene). Anisotropic structures show strong dependence on the identity of the diluents and the composition of the mixtures. Anisotropic crystal growth of the diluents was studied in terms of thermodynamics and kinetics using DSC, optical microscopy and SEM. Microstructures of the porous materials were explained in terms of supercooling and dendritic solidification. Dual functionality of the crystallizable diluents for composite materials was evaluated using isotactic polypropylene (iPP) and compatible diluents that crystallize upon cooling. The selected diluents form homogeneous mixtures with iPP at high temperature and lower the viscosity (improved processability), which undergo phase separation upon cooling to form solid particles that function as a toughening agent at room temperature. Tensile properties and morphology of the composites showed that organic crystalline particles have the similar effect as rigid particles to increase toughness; de-wetting between the particle and iPP matrix occurs at the early stage of deformation, followed by unhindered plastic flow that consumes significant amount of fracture energy. The effect of the diluents, however, strongly depends on the identity of the diluents that interact with the iPP during solidification step, which was demonstrated by comparing tetrabromobisphenol-A and phthalic anhydride. A simple method to prepare composite surfaces that can change the wettability in response to the temperature change was proposed and evaluated. Composite surfaces prepared by nanoporous alumina templates filled with polymers showed surface morphology and wettability that depend on temperature. This effect is attributed to the significant difference in thermal conductivity and the thermal expansion coefficient between the alumina and the polymers. The reversibility in thermal response depends on the properties of the polymers.

Poly(vinylidene fluoride)-La(0.5)Sr(0.5)CoO(3-δ) composites: the influence of LSCO particle size on the structure and dielectric properties.

PubMed

Deepa, K S; Shaiju, P; Sebastian, M T; Gowd, E Bhoje; James, J

2014-08-28

Dielectric composites composed of poly(vinylidene fluoride) (PVDF) and La0.5Sr0.5CoO3-δ (LSCO) with high permittivity, low loss and high breakdown strength have been developed. The effects of particle size of LSCO (fine (∼250 nm) and coarse (∼3 μm)) on the phase crystallization of PVDF and dielectric properties of polymer-LSCO composites are studied. The inclusion of fine LSCO into PVDF readily favours the formation of polar crystals (β and γ-phases), which makes the composite suitable for both electromechanical and high charge storage embedded capacitor applications. Moreover, the addition of fine LSCO particles also increases the overall crystallization rate as well as the melting point of PVDF. The composite containing fine LSCO particles gave a percolation threshold at about 25 volume percentage, while that with coarse particles did not show any percolation even at very high volume percentage. As a result of fine LSCO particle loading, the composite exhibited a relative permittivity (εr) of ∼600, a conductivity of 2.7 × 10(-7) S cm(-1), a dielectric loss (tan δ) of 0.7 at 1 kHz and a breakdown voltage of 100 V even at 20 volume percentage of a filler, demonstrating promising applications in the embedded capacitors.

Compositional segregation and electrical properties characterization of [001]- and [011]-oriented co-growth Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystal

NASA Astrophysics Data System (ADS)

Song, Kexin; Li, Zhenrong; Guo, Haisheng; Xu, Zhuo; Fan, Shiji

2018-04-01

A Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 relaxor ferroelectric single crystal boule of 3 in. diameter was grown using [001]- and [011]-oriented co-growth crystals as seeds by the modified Bridgman method. The as-grown crystal boule was divided into two growth regions [001] and [011]. The composition and the electrical properties of samples of the two regions were characterized in detail along the growth direction in the whole crystal boule. The PT content of [001]-grown samples increased from 27.7 to 36.8 mol. % along the growth direction, especially they are averagely higher about 0.7 mol. % than those of [011]-grown samples at the same growth position. The PMN content of [001]-grown samples decreased from 43.0 to 34.8 mol. %, which is lower than that of the corresponding [011]-grown samples. The compositional segregation behavior along [001] and [011] growth directions was discussed based on the crystal growth theories. Variations in the rhombohedral to tetragonal phase transition temperature (TRT), the piezoelectric properties, the coercive electric field and the remnant polarization of [001] samples were discussed according to changes in compositional segregation and crystal anisotropy. Under the exact same growth conditions, the [011]-grown crystal has a larger composition segregation effect than that of the [001]-grown crystal. This result provides a positive effect on analysing the nature and reducing the effect of compositional segregation.

Solidification and crystal growth of solid solution semiconducting alloys

NASA Technical Reports Server (NTRS)

Lehoczky, S. L.; Szofran, F. R.

1984-01-01

Problems associated with the solidification and crytal growth of solid-solution semiconducting alloy crystals in a terrestrial environment are described. A detailed description is given of the results for the growth of mercury cadmium telluride (HgCdTe) alloy crystals by directional solidification, because of their considerable technological importance. A series of HgCdTe alloy crystals are grown from pseudobinary melts by a vertical Bridgman method using a wide range of growth rates and thermal conditions. Precision measurements are performed to establish compositional profiles for the crystals. The compositional variations are related to compositional variations in the melts that can result from two-dimensional diffusion or density gradient driven flow effects ahead of the growth interface. These effects are discussed in terms of the alloy phase equilibrium properties, the recent high temperature thermophysical data for the alloys and the highly unusual heat transfer characteristics of the alloy/ampule/furnace system that may readily lead to double diffusive convective flows in a gravitational environment.

Effect of grain-boundary crystallization on the high-temperature strength of silicon nitride

NASA Technical Reports Server (NTRS)

Pierce, L. A.; Mieskowski, D. M.; Sanders, W. A.

1986-01-01

Si3N4 specimens having the composition 88.7 wt pct Si3N4-4.9 wt pct SiO2-6.4 wt pct Y2O3 were sintered at 2140 C under 25 atm N2 for 1 h and then subjected to a 5 h anneal at 1500 C. Crystallization of an amorphous grain-boundary phase resulted in the formation of Y2Si2O7. The short-time 1370 C strength of this material was compared with that of material of the same composition having no annealing treatment. No change in strength was noted. This is attributed to the refractory nature of the yttrium-rich grain-boundary phase (apparently identical in both glassy and crystalline phases) and the subsequent domination of the failure process by common processing flaws.

Dislocation dynamics and crystal plasticity in the phase-field crystal model

NASA Astrophysics Data System (ADS)

Skaugen, Audun; Angheluta, Luiza; Viñals, Jorge

2018-02-01

A phase-field model of a crystalline material is introduced to develop the necessary theoretical framework to study plastic flow due to dislocation motion. We first obtain the elastic stress from the phase-field crystal free energy under weak distortion and show that it obeys the stress-strain relation of linear elasticity. We focus next on dislocations in a two-dimensional hexagonal lattice. They are composite topological defects in the weakly nonlinear amplitude equation expansion of the phase field, with topological charges given by the standard Burgers vector. This allows us to introduce a formal relation between the dislocation velocity and the evolution of the slowly varying amplitudes of the phase field. Standard dissipative dynamics of the phase-field crystal model is shown to determine the velocity of the dislocations. When the amplitude expansion is valid and under additional simplifications, we find that the dislocation velocity is determined by the Peach-Koehler force. As an application, we compute the defect velocity for a dislocation dipole in two setups, pure glide and pure climb, and compare it with the analytical predictions.

Phase conversion from hexagonal CuS(y)Se(1-y) to cubic Cu(2-x)S(y)Se(1-y): composition variation, morphology evolution, optical tuning, and solar cell applications.

PubMed

Xu, Jun; Yang, Xia; Yang, Qingdan; Zhang, Wenjun; Lee, Chun-Sing

2014-09-24

In this work, we report a simple and low-temperature approach for the controllable synthesis of ternary Cu-S-Se alloys featuring tunable crystal structures, compositions, morphologies, and optical properties. Hexagonal CuS(y)Se(1-y) nanoplates and face centered cubic (fcc) Cu(2-x)S(y)Se(1-y) single-crystal-like stacked nanoplate assemblies are synthesized, and their phase conversion mechanism is well investigated. It is found that both copper content and chalcogen composition (S/Se atomic ratio) of the Cu-S-Se alloys are tunable during the phase conversion process. Formation of the unique single-crystal-like stacked nanoplate assemblies is resulted from oriented stacking coupled with the Ostwald ripening effect. Remarkably, optical tuning for continuous red shifts of both the band-gap absorption and the near-infrared localized surface plasmon resonance are achieved. Furthermore, the novel Cu-S-Se alloys are utilized for the first time as highly efficient counter electrodes (CEs) in quantum dot sensitized solar cells (QDSSCs), showing outstanding electrocatalytic activity for polysulfide electrolyte regeneration and yielding a 135% enhancement in power conversion efficiency (PCE) as compared to the noble metal Pt counter electrode.

Priority compositions of boron carbide crystals obtained by self-propagating high-temperature synthesis

NASA Astrophysics Data System (ADS)

Ponomarev, V. I.; Konovalikhin, S. V.; Kovalev, I. D.; Vershinnikov, V. I.

2015-09-01

Splitting of reflections from boron carbide has been found for the first time by an X-ray diffraction study of polycrystalline mixture of boron carbide В15- х С х , (1.5 ≤ x ≤ 3) and its magnesium derivative C4B25Mg1.42. An analysis of reflection profiles shows that this splitting is due to the presence of boron carbide phases of different compositions in the sample, which are formed during crystal growth. The composition changes from В12.9С2.1 to В12.4С2.6.

Effect of heat treatment on surface hydrophilicity-retaining ability of titanium dioxide nanotubes

NASA Astrophysics Data System (ADS)

Sun, Yu; Sun, Shupei; Liao, Xiaoming; Wen, Jiang; Yin, Guangfu; Pu, Ximing; Yao, Yadong; Huang, Zhongbing

2018-05-01

The aim of this study is to investigate the effect of different annealing temperature and atmosphere on the surface wettability retaining properties of titania nanotubes (TNs) fabricated by anodization. The TNs morphology, crystal phase composition and surface elemental composition and water contact angle (WCA) were investigated by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and contact angle instrument, respectively. After the samples annealed at 200 °C, 450 °C, 850 °C have been stored in air for 28 days, the WCAs increase to 31.7°, 21.1° and 110.5°, respectively. The results indicate that crystal phase composition of TNs plays an important role in surface wettability. Compared with the WCA (21.1°) of the samples annealed in air after 28 days, the WCA of samples annealed in oxygen-deficient atmosphere is lower, suggesting the contribution of oxygen vacancy in the enhanced hydrophilicity-retaining ability. Our study demonstrates that the surface hydrophilicity-retaining ability of TNs is related to the ordered nanotubular structure, crystal structure, the amount of surface hydroxyl group and oxygen vacancy defects.

Semicrystalline Ionomer-Metal Carboxylate Composite: Phase Behavior and Mechanical Properties

NASA Astrophysics Data System (ADS)

Wakabayashi, Katsuyuki

2005-03-01

We have shown previously that the thermal and mechanical behavior of ethylene-methacrylic acid (E-MAA) ionomers can be tuned by the addition of certain magnesium carboxylates, such as magnesium stearate (MgSt). The property modifications result from coassembly of the two components, both co-aggregation of the ionic groups and co-crystallization of the methylene sequences, as revealed by X-ray scattering. When MgSt is replaced by sodium stearate (NaSt), a different suite of mechanical properties is obtained. NaSt, with its high melting and clearing (288 ^oC) points, readily crystallizes out of solution in the molten polymer and forms an effective composite upon cooling from a single-phase melt. The NaSt crystals in the composite resemble the rectangular polymorph in pure NaSt, though with some differences in lattice parameters and transition temperatures due to interaction with the acid groups of the copolymer. The different physical properties of the NaSt vs. MgSt modified ionomers are traced to these microstructural differences, elucidated through a combination of X-ray scattering and microscopy.

The petrologic history of the Sanganguey volcanic field, Nayarit, Mexico: Comparisons in a suite of crystal-rich and crystal-poor lavas

NASA Astrophysics Data System (ADS)

Crabtree, Stephen M.; Waters, Laura E.

2017-04-01

To evaluate if intermediate magmas erupting from Volcán Sanganguey (Mexico) and the surrounding volcanic field are formed by mixing of basalts and rhyolites or if they initially exist as intermediate liquids, a detailed petrological study is presented for eight andesite and dacite magmas. Six of the samples erupted from the central edifice (four andesites and two dacites) are crystal-rich (≤ 50 vol%), whereas the remaining two samples (one andesite and one dacite) erupted from monogenetic vents in the peripheral volcanic field and are crystal poor (≤ 5 vol%). Despite the variation in crystallinity, all samples are multiply saturated in five to seven mineral phases (plagioclase + orthopyroxene + titanomagnetite + ilmenite + apatite ± clinopyroxene ± hornblende). In all samples, plagioclase spans a 30-40 mol% An range in composition and orthopyroxene spans a range in Mg# of 5-10. Pre-eruptive temperatures and oxygen fugacites (relative to the NNO buffer) range from 853 (± 24) to 1085 (± 16) °C and - 0.1 (± 0.1) to 0.9 (± 0.1) Δ NNO, on the basis of Fe-Ti two oxide thermometry. Application of the plagioclase-liquid hygrometer to the samples reveals maximum H2O contents that range from 1.7-6.2 wt%. Comparison with phase equilibrium experiments demonstrates that all plagioclase and orthopyroxene compositions in the crystal-poor samples could have grown from their respective whole rock compositions. Comparison of crystal rich samples with phase equilibrium experiments reveals the presence of sodic xenocrysts which reflect resorption textures and an estimated excess plagioclase crystal cargo of > 6 vol%. The excess plagioclase crystal cargo is not distinguishable from phenocrystic plagioclase based on composition or texture, suggesting that they were also grown in intermediate melts, and are therefore described as antecrystic. No calcic plagioclase xenocrysts (> An79) typical of hydrous arc basalts are observed, thus it is likely that the excess plagioclase in the crystal-rich samples were originally formed in intermediate magmas. For the crystal-poor samples, we propose that the mechanism producing the complex phenocryst assemblages is degassing (± cooling), as it may shift equilibrium plagioclase compositions, kinetically inhibit crystal-growth, and increase melt viscosity, leading to complex textures. Notably, the hypothesis of degassing (± cooling) induced crystallization requires that the intermediate melts initially exist as liquids, prior to crystallization, supporting the hypothesis that intermediate melts are generated in the deep crust and arrive in the upper crust as liquids. For the crystal-rich samples, degassing (± cooling) may also be the mechanism generating a portion of the compositional and textural variation in the mineral assemblages and some incorporation of antecrysts or xenocrysts must occur as evidenced by an excess plagioclase crystal cargo; however, we find no definitive evidence supporting the incorporation of crystals initially grown in basalts or rhyolites. Given the similarities in phase assemblage, mineral compositions, mineral textures, and intensive variables between the crystal-poor and -rich samples, we conclude that the melts arriving into the upper crust beneath Volcán Sanganguey and the surrounding peripheral volcanic field are intermediate in composition and are initially formed (as liquids) in the deep crust. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-103. Appendix Fig. B.2.3. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-117. Appendix Fig. B.2.4. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-109. Appendix Fig. B.2.5. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-132. Appendix Fig. B.2.6. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-115. Appendix Fig. B.2.7. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-106. Appendix Fig. B.2.8. Plots of plagioclase composition (%An) vs. distance across each grain, XAL-129. Appendix Fig. B.3.2. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-103. Appendix Fig. B.3.3. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-117 Appendix Fig. B.3.4. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-109. Appendix Fig. B.3.5. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-132. Appendix Fig. B.3.6. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-115. Appendix Fig. B.3.7. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-106. Appendix Fig. B.3.8. Plots of pyroxene composition (Mg#) vs. distance across each grain, XAL-129. Appendix Fig. B.4.2. BSE images of plagioclase grains, with traversal path indicated, XAL-103. Appendix Fig. B.4.3. BSE images of plagioclase grains, with traversal path indicated, XAL-117. Appendix Fig. B.4.4. BSE images of plagioclase grains, with traversal path indicated, XAL-109. Appendix Fig. B.4.5. BSE images of plagioclase grains, with traversal path indicated, XAL-132. Appendix Fig. B.4.6. BSE images of plagioclase grains, with traversal path indicated, XAL-115. Appendix Fig. B.4.7. BSE images of plagioclase grains, with traversal path indicated, XAL-106. Appendix Fig. B.4.8. BSE images of plagioclase grains, with traversal path indicated, XAL-129. Appendix Fig. B.5.2. BSE images of pyroxene grains, with traversal path indicated, XAL-103. Appendix Fig. B.5.3. BSE images of pyroxene grains, with traversal path indicated, XAL-117. Appendix Fig. B.5.4. BSE images of pyroxene grains, with traversal path indicated, XAL-109. Appendix Fig. B.5.5. BSE images of pyroxene grains, with traversal path indicated, XAL-132. Appendix Fig. B.5.6. BSE images of pyroxene grains, with traversal path indicated, XAL-115. Appendix Fig. B.5.7. BSE images of pyroxene grains, with traversal path indicated, XAL-106. Appendix Fig. B.5.8. BSE images of pyroxene grains, with traversal path indicated, XAL-129.

Phase Composition Maps integrate mineral compositions with rock textures from the micro-meter to the thin section scale

NASA Astrophysics Data System (ADS)

Willis, Kyle V.; Srogi, LeeAnn; Lutz, Tim; Monson, Frederick C.; Pollock, Meagen

2017-12-01

Textures and compositions are critical information for interpreting rock formation. Existing methods to integrate both types of information favor high-resolution images of mineral compositions over small areas or low-resolution images of larger areas for phase identification. The method in this paper produces images of individual phases in which textural and compositional details are resolved over three orders of magnitude, from tens of micrometers to tens of millimeters. To construct these images, called Phase Composition Maps (PCMs), we make use of the resolution in backscattered electron (BSE) images and calibrate the gray scale values with mineral analyses by energy-dispersive X-ray spectrometry (EDS). The resulting images show the area of a standard thin section (roughly 40 mm × 20 mm) with spatial resolution as good as 3.5 μm/pixel, or more than 81 000 pixels/mm2, comparable to the resolution of X-ray element maps produced by wavelength-dispersive spectrometry (WDS). Procedures to create PCMs for mafic igneous rocks with multivariate linear regression models for minerals with solid solution (olivine, plagioclase feldspar, and pyroxenes) are presented and are applicable to other rock types. PCMs are processed using threshold functions based on the regression models to image specific composition ranges of minerals. PCMs are constructed using widely-available instrumentation: a scanning-electron microscope (SEM) with BSE and EDS X-ray detectors and standard image processing software such as ImageJ and Adobe Photoshop. Three brief applications illustrate the use of PCMs as petrologic tools: to reveal mineral composition patterns at multiple scales; to generate crystal size distributions for intracrystalline compositional zones and compare growth over time; and to image spatial distributions of minerals at different stages of magma crystallization by integrating textures and compositions with thermodynamic modeling.

Combining phase-field crystal methods with a Cahn-Hilliard model for binary alloys

NASA Astrophysics Data System (ADS)

Balakrishna, Ananya Renuka; Carter, W. Craig

2018-04-01

Diffusion-induced phase transitions typically change the lattice symmetry of the host material. In battery electrodes, for example, Li ions (diffusing species) are inserted between layers in a crystalline electrode material (host). This diffusion induces lattice distortions and defect formations in the electrode. The structural changes to the lattice symmetry affect the host material's properties. Here, we propose a 2D theoretical framework that couples a Cahn-Hilliard (CH) model, which describes the composition field of a diffusing species, with a phase-field crystal (PFC) model, which describes the host-material lattice symmetry. We couple the two continuum models via coordinate transformation coefficients. We introduce the transformation coefficients in the PFC method to describe affine lattice deformations. These transformation coefficients are modeled as functions of the composition field. Using this coupled approach, we explore the effects of coarse-grained lattice symmetry and distortions on a diffusion-induced phase transition process. In this paper, we demonstrate the working of the CH-PFC model through three representative examples: First, we describe base cases with hexagonal and square symmetries for two composition fields. Next, we illustrate how the CH-PFC method interpolates lattice symmetry across a diffuse phase boundary. Finally, we compute a Cahn-Hilliard type of diffusion and model the accompanying changes to lattice symmetry during a phase transition process.

An abrupt change in the magmatic source of rhyolite volcanism in Long Valley, CA recorded by pre-eruptive oxygen fugacities of the Early Rhyolites (Obsidians): evidence of transition from subduction-modified lithosphere to asthenosphere

NASA Astrophysics Data System (ADS)

Waters, L.; Lange, R. A.

2016-12-01

Detailed mapping of the Long Valley (CA) region (Hildreth, 2004) reveals that the eruption of the Late Bishop Tuff (LBT) is followed by eruption of the Early Rhyolites (ER), which are obsidian lavas. The obsidians are paradoxical, as they erupted effusively, contain multiple phases (some of which vary in composition), and yet, they are crystal-poor. The obsidians are saturated in ≥7 phases (plagioclase + orthopyroxene + ilmenite + titanomagnetite + biotite + apatite + zircon ± pyrrhotite). Plagioclase and orthopyroxene crystals have rounded edges accompanying euhedral margins, and large (>200µm) ilmenites have swallow-tail growth. Plagioclase and orthopyroxene span a compositional range between An20-45 and En43-58, respectively, and phase equilibrium experiments confirm that these are phenocrysts, despite their complex textures. Pre-eruptive temperatures and fO2 values are calculated applying Fe-Ti oxide thermometry to all possible oxide pairs and range from 724-861°C and ΔNNO -0.3 to -0.9, respectively. Application of the plagioclase hygrometer to crystals in ER obsidians reveals pre-eruptive H2O contents of 3-5wt%. We propose that mineral compositions and textures within the ER obsidians record rapid growth due to degassing-induced crystallization of a superheated melt. Superheating is required to explain the origin of the ER lavas as it eliminates nucleation sites, requiring crystallization to occur on nuclei that form during degassing enabling effusive eruption of crystal-poor lavas. The ER obsidians differ from the LBT in their crystallinities (<5% vs. >12%), phenocryst phases (e.g., sanidine is absent in ER obsidians), plagioclase compositions (An20-45 vs. An20-29), and fO2 values (ΔNNO < -0.3 vs. +0.5), which suggests that the ER lavas may not be derived from the LBT reservoir. Rather, we hypothesize that the ER phenocryst assemblage, reduced fO2 values, and requirement for superheating can be explained if the obsidians formed as partial melts of a mixed lithology, consisting of pre-existing crust and an additional component with low fO2. We propose that the reduced component in the ER source is aesthenospheric basalt, which suggests that a transition in mantle source, from subduction-modified lithosphere to asthenosphere, has occurred beneath Long Valley.

Crystal Growth of II-VI Semiconducting Alloys by Directional Solidification

NASA Technical Reports Server (NTRS)

Lehoczky, Sandor L.; Szofran, Frank R.; Su, Ching-Hua; Cobb, Sharon D.; Scripa, Rosalia A.; Sha, Yi-Gao

1999-01-01

This research study is investigating the effects of a microgravity environment during the crystal growth of selected II-VI semiconducting alloys on their compositional, metallurgical, electrical and optical properties. The on-going work includes both Bridgman-Stockbarger and solvent growth methods, as well as growth in a magnetic field. The materials investigated are II-VI, Hg(1-x)Zn(x)Te, and Hg(1-x)Zn(x)Se, where x is between 0 and 1 inclusive, with particular emphasis on x-values appropriate for infrared detection and imaging in the 5 to 30 micron wavelength region. Wide separation between the liquidus and solidus of the phase diagrams with consequent segregation during solidification and problems associated with the high volatility of one of the components (Hg), make the preparation of homogeneous, high-quality, bulk crystals of the alloys an extremely difficult nearly an impossible task in a gravitational environment. The three-fold objectives of the on-going investigation are as follows: (1) To determine the relative contributions of gravitationally-driven fluid flows to the compositional redistribution observed during the unidirectional crystal growth of selected semiconducting solid solution alloys having large separation between the liquidus and solidus of the constitutional phase diagram; (2) To ascertain the potential role of irregular fluid flows and hydrostatic pressure effects in generation of extended crystal defects and second-phase inclusions in the crystals; and, (3) To obtain a limited amount of "high quality" materials needed for bulk crystal property characterizations and for the fabrication of various device structures needed to establish ultimate material performance limits. The flight portion of the study was to be accomplished by performing growth experiments using the Crystal Growth Furnace (CGF) manifested to fly on various Spacelab missions.

Optical sensor platform based on cellulose nanocrystals (CNC) - 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC) bi-phase nematic liquid crystal composite films.

PubMed

Santos, Moliria V; Tercjak, Agnieszka; Gutierrez, Junkal; Barud, Hernane S; Napoli, Mariana; Nalin, Marcelo; Ribeiro, Sidney J L

2017-07-15

The preparation of composite materials has gained tremendous attention due to the potential synergy of the combined materials. Here we fabricate novel thermal/electrical responsive photonic composite films combining cellulose nanocrystals (CNC) with a low molecular weight nematic liquid crystal (NLC), 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC). The obtained composite material combines both intense structural coloration of photonic cellulose and thermal and conductive properties of NLC. Scanning electron microscopy (SEM) results confirmed that liquid crystals coated CNC films maintain chiral nematic structure characteristic of CNC film and simultaneously, transversal cross-section scanning electron microscopy images indicated penetration of liquid crystals through the CNC layers. Investigated composite film maintain NLC optical properties being switchable as a function of temperature during heating/cooling cycles. The relationship between the morphology and thermoresponsive in the micro/nanostructured materials was investigated by using transmission optical microscopy (TOM). Conductive response of the composite films was proved by Electrostatic force microscopy (EFM) measurement. Designed thermo- and electro-responsive materials open novel simple pathway of fabrication of CNC-based materials with tunable properties. Copyright © 2017. Published by Elsevier Ltd.

Lyotropic liquid crystal engineering moving beyond binary compositional space - ordered nanostructured amphiphile self-assembly materials by design.

PubMed

van 't Hag, Leonie; Gras, Sally L; Conn, Charlotte E; Drummond, Calum J

2017-05-22

Ordered amphiphile self-assembly materials with a tunable three-dimensional (3D) nanostructure are of fundamental interest, and crucial for progressing several biological and biomedical applications, including in meso membrane protein crystallization, as drug and medical contrast agent delivery vehicles, and as biosensors and biofuel cells. In binary systems consisting of an amphiphile and a solvent, the ability to tune the 3D cubic phase nanostructure, lipid bilayer properties and the lipid mesophase is limited. A move beyond the binary compositional space is therefore required for efficient engineering of the required material properties. In this critical review, the phase transitions upon encapsulation of more than 130 amphiphilic and soluble additives into the bicontinuous lipidic cubic phase under excess hydration are summarized. The data are interpreted using geometric considerations, interfacial curvature, electrostatic interactions, partition coefficients and miscibility of the alkyl chains. The obtained lyotropic liquid crystal engineering design rules can be used to enhance the formulation of self-assembly materials and provides a large library of these materials for use in biomedical applications (242 references).

Liquidus Phases of the Richardson H5 Chondrite at High Pressures and Temperatures

NASA Technical Reports Server (NTRS)

Channon, M.; Garber, J.; Danielson, L. R.; Righter, K.

2007-01-01

Part of early mantle evolution may include a magma ocean, where core formation began before the proto-Earth reached half of its present radius. Temperatures were high and bombardment and accretion were still occurring, suggesting that the proto-Earth consisted of a core and an at least partially liquid mantle, the magma ocean. As the Earth accreted, pressure near the core increased and the magma ocean decreased in volume and became shallower as it began to cool and solidify. As crystals settled, or floated, the composition of the magma ocean could change significantly and begin to crystallize different minerals from the residual liquid. Therefore, the mantle may be stratified following the P-T phase diagram for the bulk silicate Earth. To understand mantle evolution, it is necessary to know liquidus phase relations at high pressures and temperatures. In order to model the evolution of the magma ocean, high pressure and temperature experiments have been conducted to simulate the crystallization process using a range of materials that most likely resemble the bulk composition of the early Earth.

Sustainable thermoelectric materials fabricated by using Cu2Sn1-xZnxS3 nanoparticles as building blocks

NASA Astrophysics Data System (ADS)

Zhou, Wei; Shijimaya, Chiko; Takahashi, Mari; Miyata, Masanobu; Mott, Derrick; Koyano, Mikio; Ohta, Michihiro; Akatsuka, Takeo; Ono, Hironobu; Maenosono, Shinya

2017-12-01

Uniform Cu2Sn1-xZnxS3 (x = 0-0.2) nanoparticles (NPs) with a characteristic size of about 40 nm were chemically synthesized. The primary crystal phase of the NPs was wurtzite (WZ) with a mean crystalline size of about 20 nm. The NPs were sintered to form nanostructured pellets with different compositions preserving the composition and grain size of the original NPs by the pulse electric current sintering technique. The pellets had a zinc blende (ZB) structure with a residual WZ phase, and the mean crystalline size was found to remain virtually unchanged for all pellets. Among all samples, the pellets of Cu2Sn0.95Zn0.05S3 and Cu2Sn0.85Zn0.15S3 exhibited the highest ZT value (0.37 at 670 K) which is 10 times higher than that of a non-nanostructured Cu2SnS3 bulk crystal thanks to effective phonon scattering by nanograins, the phase-pure ZB crystal structure, and the increase in hole carrier density by Zn doping.

Crystallization kinetics of BaO-Al2O3-SiO2 glasses

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.

1989-01-01

Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt percent) 10BaO-38Al2O3-51SiO2-1MoO3 (glass A) and 39BaO-25Al2O3-35SiO2-1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3-2SiO2) and hexacelsian (BaO-Al2O3-2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 C. It undergoes structural transformation into the orthorhombic form at approximately 300 C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.

Crystallization kinetics of BaO-Al2O3-SiO2 glasses

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Hyatt, Mark J.

1988-01-01

Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt percent) 10BaO-38Al2O3-51SiO2-1MoO3 (glass A) and 39BaO-25Al2O3-35SiO2-1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3-2SiO2) and hexacelsian (BaO-Al2O3-2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 C. It undergoes structural transformation into the orthorhombic form at approximately 300 C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.

Room temperature metastable monoclinic phase in BaTiO3 crystals

NASA Astrophysics Data System (ADS)

Lummen, Tom; Wang, Jianjun; Holt, Martin; Kumar, Amit; Vlahos, Eftihia; Denev, Sava; Chen, Long-Qing; Gopalan, Venkatraman

2011-03-01

Low-symmetry monoclinic phases in ferroelectric materials are of considerable interest, due to their associated enhanced electromechanical coupling. Such phases have been found in Pb-based perovskite solid solutions such as lead zirconate titanate (PZT), where they form structural bridges between the rhombohedral and tetragonal ground states in compositional space. In this work, we directly image such a monoclinic phase in BaTi O3 crystals at room-temperature, using optical second harmonic generation, Raman, and X-ray microscopic imaging techniques. Phase-field modeling indicates that ferroelectric domain microstructures in BaTi O3 induce local inhomogeneous stresses in the crystals, which can effectively trap the transient intermediate monoclinic structure that occurs across the thermal orthorhombic-tetragonal phase boundary. The induced metastable monoclinic domains are ferroelectrically soft, being easily moved by electric fields as low as 0.5 kV cm-1 . Stabilizing such intermediate low-symmetry phases could very well lead to Pb-free materials with enhanced piezoelectric properties.

Dependences of the density of M 1- x R x F2 + x and R 1- y M y F3- y single crystals ( M = Ca, Sr, Ba, Cd, Pb; R means rare earth elements) on composition

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Krivandina, E. A.; Zhmurova, Z. I.

2013-11-01

The density of single crystals of nonstoichiometric phases Ba1 - x La x F2 + x (0 ≤ x ≤ 0.5) and Sr0.8La0.2 - x Lu x F2.2 (0 ≤ x ≤ 0.2) with the fluorite (CaF2) structure type and R 1 - y Sr y F3 - y ( R = Pr, Nd; 0 ≤ y ≤ 0.15) with the tysonite (LaF3) structure type has been measured. Single crystals were grown from a melt by the Bridgman method. The measured concentration dependences of single crystal density are linear. The interstitial and vacancy models of defect formation in the fluorite and tysonite phases, respectively, are confirmed. To implement the composition control of single crystals of superionic conductors M 1 - x R x F2 + x and R 1 - y M y F3 - y in practice, calibration graphs of X-ray density in the MF2- RF3 systems ( M = Ca, Sr, Ba, Cd, Pb; R = La-Lu, Y) are plotted.

Spinodal decomposition of the gamma-phase upon quenching in the Ti-Al-Nb ternary

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rios, Orlando; Ebrahimi, Fereshteh

2010-01-01

The {gamma}-TiAl with L1{sub 0} crystal structure shows extensive solubility for Nb at elevated temperatures. Recently (Rios et al., Acta materialia 2009; 57:6243), we have demonstrated that the high-Nb {gamma}-TiAl phase becomes unstable upon rapid cooling into a nano-scale two-phase microstructure. In this paper, using detailed compositional and microstructural analyses, we have demonstrated that this phase goes through a spinodal decomposition that results in the compositionally distinct phases identified as a lower-Nb {gamma}-phase and the h-phase, which is rich in Nb and forms by the ordering of this element in the {gamma}-phase.

Crystal viscoplasticity model for the creep-fatigue interactions in single-crystal Ni-base superalloy CMSX-8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Estrada Rodas, Ernesto A.; Neu, Richard W.

A crystal viscoplasticity (CVP) model for the creep-fatigue interactions of nickel-base superalloy CMSX-8 is proposed. At the microstructure scale of relevance, the superalloys are a composite material comprised of a γ phase and a γ' strengthening phase with unique deformation mechanisms that are highly dependent on temperature. Considering the differences in the deformation of the individual material phases is paramount to predicting the deformation behavior of superalloys at a wide range of temperatures. In this work, we account for the relevant deformation mechanisms that take place in both material phases by utilizing two additive strain rates to model the deformationmore » on each material phase. The model is capable of representing the creep-fatigue interactions in single-crystal superalloys for realistic 3-dimensional components in an Abaqus User Material Subroutine (UMAT). Using a set of material parameters calibrated to superalloy CMSX-8, the model predicts creep-fatigue, fatigue and thermomechanical fatigue behavior of this single-crystal superalloy. In conclusion, a sensitivity study of the material parameters is done to explore the effect on the deformation due to changes in the material parameters relevant to the microstructure.« less

Crystal viscoplasticity model for the creep-fatigue interactions in single-crystal Ni-base superalloy CMSX-8

DOE PAGES

Estrada Rodas, Ernesto A.; Neu, Richard W.

2017-09-11

A crystal viscoplasticity (CVP) model for the creep-fatigue interactions of nickel-base superalloy CMSX-8 is proposed. At the microstructure scale of relevance, the superalloys are a composite material comprised of a γ phase and a γ' strengthening phase with unique deformation mechanisms that are highly dependent on temperature. Considering the differences in the deformation of the individual material phases is paramount to predicting the deformation behavior of superalloys at a wide range of temperatures. In this work, we account for the relevant deformation mechanisms that take place in both material phases by utilizing two additive strain rates to model the deformationmore » on each material phase. The model is capable of representing the creep-fatigue interactions in single-crystal superalloys for realistic 3-dimensional components in an Abaqus User Material Subroutine (UMAT). Using a set of material parameters calibrated to superalloy CMSX-8, the model predicts creep-fatigue, fatigue and thermomechanical fatigue behavior of this single-crystal superalloy. In conclusion, a sensitivity study of the material parameters is done to explore the effect on the deformation due to changes in the material parameters relevant to the microstructure.« less

Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization

NASA Astrophysics Data System (ADS)

Prokofiev, A.; Yan, X.; Ikeda, M.; Löffler, S.; Paschen, S.

2014-09-01

We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46-x and Ba8Cu4.8GaxGe41.2-x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41 and Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.

Crystallization of Na2O-SiO2 gel and glass

NASA Technical Reports Server (NTRS)

Neilson, G. F.; Weinberg, M. C.

1984-01-01

The crystallization behavior of a 19 wt pct soda silica gel and gel-derived glass was compared to that of the ordinary glass of the same composition. Both bulk and ground glass samples were utilized. X-ray diffraction measurements were made to identify the crystalline phases and gauge the extent of crystallization. It was found that the gel crystallized in a distinctive manner, while the gel glass behavior was not qualitatively different from that of the ordinary glass.

Analysis of Crystallization Kinetics

NASA Technical Reports Server (NTRS)

Kelton, Kenneth F.

1997-01-01

A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.

Multicomponent homogeneous alloys and method for making same

DOEpatents

Dutta, Partha S.; Miller, Thomas R.

2003-09-02

The present application discloses a method for preparing a homogeneous ternary or quaternary alloy from a quaternary melt. The method includes providing a family of phase diagrams for the quaternary melt which shows (i) composition/temperature data, (ii) tie lines connecting equilibrium liquid and solid compositions, and (iii) isotherms representing boundaries of a miscibility gap. Based on the family of phase diagrams, a quaternary melt composition and an alloy growth temperature is selected. A quaternary melt having the selected quaternary melt composition is provided and a ternary or quaternary alloy is grown from the quaternary melt at the selected alloy growth temperature. A method for making homogeneous ternary or quaternary alloy from a ternary or quaternary melt is also disclosed, as are homogeneous quaternary single-crystal alloys which are substantially free from crystal defects and which have the formula A.sub.x B.sub.1-x C.sub.y D.sub.1-y, x and y being the same or different and in the range of 0.001 to 0.999.

Fabrication and secondary-phase crystallization of rare-earth disilicate-silicon nitride ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinibulk, M.K.; Thomas, G.; Johnson, S.M.

1992-08-01

In this paper, the fabrication and intergranular-phase devitrification of silicon nitride densified with rare-earth (RE) oxide additives is investigated. The additions of the oxides of Sm, Gd, Dy, Er, and Yb, having high melting points and behaving similarly to Y[sub 2]O[sub 3], were compositionally controlled to tailor a microstructure with a crystalline secondary phase of RE[sub 2]Si[sub 2]O[sub 7]. The lanthanide oxides were found to be ass effective as Y[sub 2]O[sub 3] in densifying Si[sub 3]N[sub 4], resulting in identical microstructures and densities of 98-99% of theoretical density. The crystallization behavior of all six disilicates was similar, characterized by amore » limited nucleation and rapid growth mechanism resulting in large single crystals. Complete crystallization of the intergranular phase was obtained with the exception of a thin residual amorphous film which was observed at interfaces and believed to be rich in impurities, the cause of incomplete devitrification.« less

Direct Observation Through In Situ Transmission Electron Microscope of Early States of Crystallization in Nanoscale Metallic Glasses

NASA Astrophysics Data System (ADS)

Xie, Y.; Sohn, S.; Schroers, J.; Cha, J. J.

2017-11-01

Crystallization is a complex process that involves multiscale physics such as diffusion of atomic species over multiple length scales, thermodynamic energy considerations, and multiple possible intermediate states. In situ crystallization experiments inside a transmission electron microscope (TEM) using nanostructured metallic glasses (MGs) provide a unique platform to study directly crystallization kinetics and pathways. Here, we study the embryonic state of eutectic growth using Pt-Ni-Cu-P MG nanorods under in situ TEM. We directly observe the nucleation and growth of a Ni-rich polymorphic phase, followed by the nucleation and slower growth of a Cu-rich phase. The suppressed growth kinetics of the Cu-rich phase is attributed to locally changing chemical compositions. In addition, we show that growth can be controlled by incorporation of an entire nucleus instead of individual atoms. Such a nucleus has to align with the crystallographic orientation of a larger grain before it can be incorporated into the crystal. By directly observing the crystallization processes, particularly the early stages of non-polymorphic growth, in situ TEM crystallization studies of MG nanostructures provide a wealth of information, some of which can be applied to typical bulk crystallization.

Synthesis and characterization of Fe-Ti-Sb intermetallic compounds: Discovery of a new Slater-Pauling phase

NASA Astrophysics Data System (ADS)

Naghibolashrafi, N.; Keshavarz, S.; Hegde, Vinay I.; Gupta, A.; Butler, W. H.; Romero, J.; Munira, K.; LeClair, P.; Mazumdar, D.; Ma, J.; Ghosh, A. W.; Wolverton, C.

2016-03-01

Compounds of Fe, Ti, and Sb were prepared using arc melting and vacuum annealing. Fe2TiSb , expected to be a full Heusler compound crystallizing in the L 21 structure, was shown by XRD and SEM analyses to be composed of weakly magnetic grains of nominal composition Fe1.5TiSb with iron-rich precipitates in the grain boundaries. FeTiSb, a composition consistent with the formation of a half-Heusler compound, also decomposed into Fe1.5TiSb grains with Ti-Sb rich precipitates and was weakly magnetic. The dominant Fe1.5TiSb phase appears to crystallize in a defective L 21 -like structure with iron vacancies. Based on this finding, a first-principles DFT-based binary cluster expansion of Fe and vacancies on the Fe sublattice of the L 21 structure was performed. Using the cluster expansion, we computationally scanned >103 configurations and predict a novel, stable, nonmagnetic semiconductor phase to be the zero-temperature ground state. This new structure is an ordered arrangement of Fe and vacancies, belonging to the space group R 3 m , with composition Fe1.5TiSb , i.e., between the full- and half-Heusler compositions. This phase can be visualized as alternate layers of L 21 phase Fe2TiSb and C 1b phase FeTiSb, with layering along the [111] direction of the original cubic phases. Our experimental results on annealed samples support this predicted ground-state composition, but further work is required to confirm that the R 3 m structure is the ground state.

Mono- and polynucleation, atomistic growth, and crystal phase of III-V nanowires under varying group V flow

NASA Astrophysics Data System (ADS)

Dubrovskii, V. G.

2015-05-01

We present a refined model for the vapor-liquid-solid growth and crystal structure of Au-catalyzed III-V nanowires, which revisits several assumptions used so far and is capable of describing the transition from mononuclear to polynuclear regime and ultimately to regular atomistic growth. We construct the crystal phase diagrams and calculate the wurtzite percentages, elongation rates, critical sizes, and polynucleation thresholds of Au-catalyzed GaAs nanowires depending on the As flow. We find a non-monotonic dependence of the crystal phase on the group V flow, with the zincblende structure being preferred at low and high group V flows and the wurtzite structure forming at intermediate group V flows. This correlates with most of the available experimental data. Finally, we discuss the atomistic growth picture which yields zincblende crystal structure and should be very advantageous for fabrication of ternary III-V nanowires with well-controlled composition and heterointerfaces.

Novel Slide-Ring Material/Natural Rubber Composites with High Damping Property

PubMed Central

Wang, Wencai; Zhao, Detao; Yang, Jingna; Nishi, Toshio; Ito, Kohzo; Zhao, Xiuying; Zhang, Liqun

2016-01-01

A novel class of polymers called “slide-ring” (SR) materials with slideable junctions were used for high damping composites for the first time. The SR acts as the high damping phase dispersed in the natural rubber (NR) matrix, and epoxidized natural rubber (ENR) acts as the compatibilizer. The morphological, structural, and mechanical properties of the composites were investigated by atomic force microscope (AFM), transmission electron microscope (TEM), dynamic mechanical thermal analyzer (DMTA), rubber processing analyzer (RPA), and tensile tester. AFM and TEM results showed that the SR phase was uniformly dispersed in the composites, in a small size that is a function of ENR. DMTA and RPA results showed that the damping factor of the composites is much higher than that of NR, especially at room temperatures. Stretch hysteresis was used to study the energy dissipation of the composites at large strains. The results showed that SR and ENR can significantly improve the dissipation efficiency at strains lower than 200% strain. Wide-angle X-ray diffraction was used to study the strain-induced crystallization of the composites. The results indicated that the impact of the SR on the crystallization of NR is mitigated by the insulating effect of ENR. PMID:26949077

Understanding metastable phase transformation during crystallization of RDX, HMX and CL-20: experimental and DFT studies.

PubMed

Ghosh, Mrinal; Banerjee, Shaibal; Shafeeuulla Khan, Md Abdul; Sikder, Nirmala; Sikder, Arun Kanti

2016-09-14

Multiphase growth during crystallization severely affects deliverable output of explosive materials. Appearance and incomplete transformation of metastable phases are a major source of polymorphic impurities. This article presents a methodical and molecular level understanding of the metastable phase transformation mechanism during crystallization of cyclic nitramine explosives, viz. RDX, HMX and CL-20. Instantaneous reverse precipitation yielded metastable γ-HMX and β-CL-20 which undergo solution mediated transformation to the respective thermodynamic forms, β-HMX and ε-CL-20, following 'Ostwald's rule of stages'. However, no metastable phase, anticipated as β-RDX, was evidenced during precipitation of RDX, which rather directly yielded the thermodynamically stable α-phase. The γ→β-HMX and β→ε-CL-20 transformations took 20 and 60 minutes respectively, whereas formation of α-RDX was instantaneous. Density functional calculations were employed to identify the possible transition state conformations and to obtain activation barriers for transformations at wB97XD/6-311++G(d,p)(IEFPCM)//B3LYP/6-311G(d,p) level of theory. The computed activation barriers and lattice energies responsible for transformation of RDX, HMX and CL-20 metastable phases to thermodynamic ones conspicuously supported the experimentally observed order of phase stability. This precise result facilitated an understanding of the occurrence of a relatively more sensitive and less dense β-CL-20 phase in TNT based melt-cast explosive compositions, a persistent and critical problem unanswered in the literature. The crystalline material recovered from such compositions revealed a mixture of β- and ε-CL-20. However, similar compositions of RDX and HMX never showed any metastable phase. The relatively long stability with the highest activation barrier is believed to restrict complete β→ε-CL-20 transformation during processing. Therefore a method is suggested to overcome this issue.

Study on dielectric and piezoelectric properties of 0.7 Pb(Mg1/3Nb2/3)O3-0.3 PbTiO3 single crystal with nano-patterned composite electrode

PubMed Central

Chang, Wei-Yi; Huang, Wenbin; Bagal, Abhijeet; Chang, Chih-Hao; Tian, Jian; Han, Pengdi; Jiang, Xiaoning

2013-01-01

Effect of nano-patterned composite electrode and backswitching poling technique on dielectric and piezoelectric properties of 0.7 Pb(Mg1/3Nb2/3)O3-0.3 PbTiO3 was studied in this paper. Composite electrode consists of Mn nano-patterns with pitch size of 200 nm, and a blanket layer of Ti/Au was fabricated using a nanolithography based lift-off process, heat treatment, and metal film sputtering. Composite electrode and backswitching poling resulted in 27% increase of d33 and 25% increase of dielectric constant, and we believe that this is attributed to regularly defined nano-domains and irreversible rhombohedral to monoclinic phase transition in crystal. The results indicate that nano-patterned composite electrode and backswitching poling has a great potential in domain engineering of relaxor single crystals for advanced devices. PMID:24170960

Phase diagram of the relaxor ferroelectric (1- x )Pb(Mg 1/3Nb 2/3)O 3+ x PbTiO 3 revisited: a neutron powder diffraction study of the relaxor skin effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phelan, D.; Rodriguez, E. E.; Gao, J.

2014-11-17

We revisit the phase diagram of the relaxor ferroelectric PMN- xPT using neutron powder diffraction to test suggestions that residual oxygen vacancies and/or strain affect the ground state crystal structure. Powdered samples of PMN- xPT were prepared with nominal compositions of x = 0:10, 0.20, 0.30, and 0.40 and divided into two identical sets, one of which was annealed in air to relieve grinding-induced strain and to promote an ideal oxygen stoichiometry. For a given composition and temperature the same structural phase is observed for each specimen. However, the distortions in all of the annealed samples are smaller than thosemore » in the as-grown samples. Further, the diffraction patterns for x = 0:10, 0.20, and 0.30 are best refined using the monoclinic Cm space group. By comparing our neutron diffraction results to those obtained on single crystals having similar compositions, we conclude that the relaxor skin effect in PMN- xPT vanishes on the Ti-rich side of the morphotropic phase boundary.« less

Characterizing new compositions of [001]C relaxor ferroelectric single crystals using a work-energy model

NASA Astrophysics Data System (ADS)

Gallagher, John A.

2016-04-01

The desired operating range of ferroelectric materials with compositions near the morphotropic phase boundary is limited by field induced phase transformations. In [001]C cut and poled relaxor ferroelectric single crystals the mechanically driven ferroelectric rhombohedral to ferroelectric orthorhombic phase transformation is hindered by antagonistic electrical loading. Instability around the phase transformation makes the current experimental technique for characterization of the large field behavior very time consuming. Characterization requires specialized equipment and involves an extensive set of measurements under combined electrical, mechanical, and thermal loads. In this work a mechanism-based model is combined with a more limited set of experiments to obtain the same results. The model utilizes a work-energy criterion that calculates the mechanical work required to induce the transformation and the required electrical work that is removed to reverse the transformation. This is done by defining energy barriers to the transformation. The results of the combined experiment and modeling approach are compared to the fully experimental approach and error is discussed. The model shows excellent predictive capability and is used to substantially reduce the total number of experiments required for characterization. This decreases the time and resources required for characterization of new compositions.

Viscoelastic damping in crystalline composites and alloys

NASA Astrophysics Data System (ADS)

Ranganathan, Raghavan; Ozisik, Rahmi; Keblinski, Pawel

We use molecular dynamics simulations to study viscoelastic behavior of model Lennard-Jones (LJ) crystalline composites subject to an oscillatory shear deformation. The two crystals, namely a soft and a stiff phase, individually show highly elastic behavior and a very small loss modulus. On the other hand, when the stiff phase is included within the soft matrix as a sphere, the composite exhibits significant viscoelastic damping and a large phase shift between stress and strain. In fact, the maximum loss modulus in these model composites was found to be about 20 times greater than that given by the theoretical Hashin-Shtrikman upper bound. We attribute this behavior to the fact that in composites shear strain is highly inhomogeneous and mostly accommodated by the soft phase, corroborated by frequency-dependent Grüneisen parameter analysis. Interestingly, the frequency at which the damping is greatest scales with the microstructural length scale of the composite. Finally, a critical comparison between damping properties of these composites with ordered and disordered alloys and superlattice structures is made.

Phase equilibria of a low S and C lunar core: Implications for an early lunar dynamo and physical state of the current core

NASA Astrophysics Data System (ADS)

Righter, K.; Go, B. M.; Pando, K. A.; Danielson, L.; Ross, D. K.; Rahman, Z.; Keller, L. P.

2017-04-01

Multiple lines of geochemical and geophysical evidence suggest the Moon has a small metallic core, yet the composition of the core is poorly constrained. The physical state of the core (now or in the past) depends on detailed knowledge of its composition, and unfortunately, there is little available data on relevant multicomponent systems (i.e., Fe-Ni-S-C) at lunar interior conditions. In particular, there is a dearth of phase equilibrium data to elucidate whether a specific core composition could help to explain an early lunar geodynamo and magnetic field intensities, or current solid inner core/liquid outer core states. We utilize geochemical information to estimate the Ni, S and C contents of the lunar core, and then carry out phase equilibria experiments on several possible core compositions at the pressure and temperature conditions relevant to the lunar interior. The first composition is 0.5 wt% S and 0.375 wt% C, based on S and C contents of Apollo glasses. A second composition contains 1 wt% each of S and C, and assumes that the lunar mantle experienced degassing of up to 50% of its S and C. Finally a third composition contains C as the dominant light element. Phase equilibrium experiments were completed at 1, 3 and 5 GPa, using piston cylinder and multi-anvil techniques. The first composition has a liquidus near 1550 °C and solidus near 1250 °C. The second composition has a narrower liquidus and solidus temperatures of 1400 and 1270 °C, respectively, while the third composition is molten down to 1150 °C. As the composition crystallizes, the residual liquid becomes enriched in S and C, but S enrichment is greater due to the incorporation of C (but not S) into solid metallic FeNi. Comparison of these results to thermal models for the Moon allow an evaluation of which composition is consistent with the geophysical data of an early dynamo and a currently solid inner and liquid outer core. Composition 1 has a high enough liquidus to start crystallizing early in lunar history (4.3 Ga), consistent with the possible core dynamo initiated by crystallization of a solid inner core. Composition 1 also stays partially molten throughout lunar history, and could easily explain the seismic data. Composition 2, on the other hand, can satisfy one or the other set of geophysical data, but not both and thus seems like a poor candidate for a lunar core composition. Composition 3 remains molten to temperatures that are lower than current estimates for the lunar core, thus ruling out the possibility of a C-rich (and S-poor) lunar core. The S- and C-poor core composition studied here (composition 1) is consistent with all available geochemical and geophysical data and provides a simple heat source and mechanism for a lunar core dynamo (core crystallization) that would obviate the need for other primary mechanisms such as impacts, core-mantle coupling, or unusual thermal histories.

Superlattice Structures, Electronic Properties, and Spin Dynamics of the Partially Cu-Extracted Phase for the Composite Crystal System CuxV4O11

NASA Astrophysics Data System (ADS)

Onoda, Masashige; Tamura, Asato

2017-02-01

The crystal structures, electronic properties, and spin dynamics of CuxV4O11 with 1.2 ≤ x < 2, classified as the partially Cu-extracted phase for the composite crystal system, are explored through measurements of x-ray four-circle diffraction, electrochemistry, electrical resistivity, thermoelectric power, magnetization, and electron paramagnetic resonance. This system has superlattice structures mainly ascribed to the partial ordering of Cu ions. Cu1.78V4O11 is triclinic with space group Pbar{1} and the double supercell of the V4O11 substructure of the composite crystal. The significantly Cu-extracted crystal Cu1.40V4O11 has a quadruple supercell with space group P1. The electron transport for V ions is nonmetallic owing to the polaronic nature and/or phonon softening and to the random potential of Cu ions. The Curie-Weiss-type paramagnetism basically originates from the Cu2+ chain coordinated octahedrally, and the EPR relaxation at low temperatures is understood through the exchange mechanism for the dipole-dipole and anisotropic exchange interactions. The near absence of paramagnetic behaviors of V4+ ions might be due to the spin-singlet ladder model or alternating-exchange chain model depending on the superlattice structure and valence distribution. The electrochemical performance of Li rechargeable batteries using this superlattice system is about 300 A h kg-1 at voltages above 2 V.

Pulsed plasma chemical synthesis of carbon-containing titanium and silicon oxide based nanocomposite

NASA Astrophysics Data System (ADS)

Kholodnaya, Galina; Sazonov, Roman; Ponomarev, Denis; Zhirkov, Igor

2018-03-01

The paper presents the results of the experimental investigation of the physical and chemical properties of the TixSiyCzOw composite nanopowders, which were first obtained using a pulsed plasma chemical method. The pulsed plasma chemical synthesis was achieved using a technological electron accelerator (TEA-500). The parameters of the electron beam are as follows: 400-450 keV electron energy, 60 ns half-amplitude pulse duration, up to 200 J pulse energy, and 5 cm beam diameter. The main physical and chemical properties of the obtained composites were studied (morphology, chemical, elemental and phase composition). The morphology of the TixSiyCzOw composites is multiform. There are large round particles, with an average size of above 150 nm. Besides, there are small particles (an average size is in the range of 15-40 nm). The morphology of small particles is in the form of crystallites. In the TixSiyCzOw synthesised composite, the peak with a maximum of 946 cm-1 was registered. The presence of IR radiation in this region of the spectrum is typical for the deformation of atomic oscillations in the Si‒О‒Ti bond, which indicates the formation of the solid solution. The composites consist of two crystal phases - anatase and rutile. The prevailing phase of the crystal structure is rutile.

Crystallization of a barium-aluminosilicate glass

NASA Technical Reports Server (NTRS)

Drummond, C. H., III; Lee, W. E.; Bansal, N. P.; Hyatt, M. J.

1989-01-01

The crystallization of a celsian glass composition was investigated as a possible high-temperature ceramic matrix material. Heat treatments invariably resulted in crystallization of the hexaclesian phase unless a flux, such as lithia, was added or a nucleating agent used (e.g., celsian seeds). TEM analysis revealed complex microstructures. Glasses with Mo additions contained hexacelsian, mullite, and an Mo-rich glass. Li2O additions stabilized celsian but mullite and Mo-rich glass were still present.

Nepheline structural and chemical dependence on melt composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marcial, José; Crum, Jarrod; Neill, Owen

Nepheline crystallizes upon slow-cooling in some melts concentrated in Na2O and Al2O3, which can result in a residual glass phase of low chemical durability. Nepheline can incorporate many components often found in high-level waste radioactive borosilicate glass, including glass network ions (e.g., Si, Al, Fe), alkali metals (e.g., Cs, K, Na, and possibly Li), alkaline-earth metals (e.g., Ba, Sr, Ca, Mg), and transition metals (e.g., Mn, and possibly Cr, Zn, Ni). When crystallized from melts of different compositions, nepheline chemistry varies as a function of starting glass composition. Five simulated high level nuclear waste borosilicate glasses shown to crystallize largemore » fractions of nepheline on slow cooling, were selected for study. These melts constituted a range of Al2O3, B2O3, CaO, Na2O, K2O, Fe2O3, and SiO2 compositions. Compositional analyses of nepheline crystals in glass by electron probe micro-analysis (EPMA) indicate that boron is unlikely to be present in any significant concentration, if at all, in nepheline. Also, several models are presented for calculating the fraction of vacancies in the nepheline structure.« less

Rhombohedrally Distorted γ-Au 5–x Zn 8+y Phases in the Au–Zn System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thimmaiah, Srinivasa; Miller, Gordon J.

2013-02-04

The region of the Au–Zn phase diagram encompassing γ-brass-type phases has been studied experimentally from 45 to 85 atom % Zn. The γ phases were obtained directly from the pure elements by heating to 680 °C in evacuated silica tubes, followed by annealing at 300 °C. Powder X-ray and single-crystal diffraction studies show that γ-“Au5Zn8” phases adopt a rhombohedrally distorted Cr5Al8 structure type rather than the cubic Cu5Zn8 type. The refined compositions from two single crystals extracted from the Zn- and Au-rich loadings are Au4.27(3)Zn8.26(3)γ0.47 (I) and Au4.58(3)Zn8.12(3)γ0.3 (II), respectively (γ = vacancy). These (I and II) refinements indicated bothmore » nonstatistical mixing of Au and Zn atoms as well as partially ordered vacancy distributions. The structures of these γ phases were solved in the acentric space group R3m (No. 160, Z = 6), and the observed lattice parameters from powder patterns were found to be a = 13.1029(6) and 13.1345(8) Å and c = 8.0410(4) and 8.1103(6) Å for crystals I and II, respectively. According to single-crystal refinements, the vacancies were found on the outer tetrahedron (OT) and octahedron (OH) of the 26-atom cluster. Single-crystal structural refinement clearly showed that the vacancy content per unit cell increases with increasing Zn, or valence-electron concentration. Electronic structure calculations, using the tight-binding linear muffin-tin orbital method with the atomic-sphere approximation (TB-LMTO-ASA) method, indicated the presence of a well-pronounced pseudogap at the Fermi level for “Au5Zn8” as the representative composition, an outcome that is consistent with the Hume–Rothery interpretation of γ brass.« less

Nonstoichiometry in inorganic fluorides: 2. Ionic conductivity of nonstoichiometric M 1 - x R xF2 + x and R 1 - y M yF3 - y crystals ( M = Ca, Sr, Ba; R are rare earth elements)

NASA Astrophysics Data System (ADS)

Sobolev, B. P.; Sorokin, N. I.

2014-11-01

The peak manifestation of nonstoichiometry in fluoride systems in the number of phases with valuable properties and wide homogeneity ranges is 45 MF2- RF3 systems, where M = Ca, Sr, Ba and R are 15 rare earth elements from La to Lu and Y (with Pm and Sc excluded). A deviation from stoichiometry in crystals of the M 1 - x R xF2 + x (CaF2 fluorite type) and R 1 - y M yF3 - y (LaF3 tysonite type) phases is responsible for the fluorine superionic conductivity σ. The range of variation in σ with changes in the qualitative ( M, R) and quantitative ( x, y) compositions in both structure types is very wide. The σ value changes by a factor of 108 in the M 1 - x R xF2 + x phases (at 500 K) and by a factor of 106 in the R 1 - y M yF3 - y phases (at 293 K). Changing compositions, one can also obtain crystals with σ values large enough for their use as fluorine-conducting solid electrolytes. Phases promising for solid electrolytes were revealed in the MFm- RFn systems ( m < n ≤ 4), which were studied within the program of searching for new multicomponent fluoride materials at the Institute of Crystallography, Russian Academy of Sciences (IC RAS). Superionic conductivity is one of the peak manifestations of the influence of defect structure of nonstoichiometric crystals on their properties. The subject of this review is the results of the studies performed at the IC RAS on the ionic conductivity of single crystals of the M 1 - x R xF2 + x and R 1 - y M yF3 - y nonstoichiometric phases.

Compositional Effects on Nickel-Base Superalloy Single Crystal Microstructures

NASA Technical Reports Server (NTRS)

MacKay, Rebecca A.; Gabb, Timothy P.; Garg,Anita; Rogers, Richard B.; Nathal, Michael V.

2012-01-01

Fourteen nickel-base superalloy single crystals containing 0 to 5 wt% chromium (Cr), 0 to 11 wt% cobalt (Co), 6 to 12 wt% molybdenum (Mo), 0 to 4 wt% rhenium (Re), and fixed amounts of aluminum (Al) and tantalum (Ta) were examined to determine the effect of bulk composition on basic microstructural parameters, including gamma' solvus, gamma' volume fraction, volume fraction of topologically close-packed (TCP) phases, phase chemistries, and gamma - gamma'. lattice mismatch. Regression models were developed to describe the influence of bulk alloy composition on the microstructural parameters and were compared to predictions by a commercially available software tool that used computational thermodynamics. Co produced the largest change in gamma' solvus over the wide compositional range used in this study, and Mo produced the largest effect on the gamma lattice parameter and the gamma - gamma' lattice mismatch over its compositional range, although Re had a very potent influence on all microstructural parameters investigated. Changing the Cr, Co, Mo, and Re contents in the bulk alloy had a significant impact on their concentrations in the gamma matrix and, to a smaller extent, in the gamma' phase. The gamma phase chemistries exhibited strong temperature dependencies that were influenced by the gamma and gamma' volume fractions. A computational thermodynamic modeling tool significantly underpredicted gamma' solvus temperatures and grossly overpredicted the amount of TCP phase at 982 C. Furthermore, the predictions by the software tool for the gamma - gamma' lattice mismatch were typically of the wrong sign and magnitude, but predictions could be improved if TCP formation was suspended within the software program. However, the statistical regression models provided excellent estimations of the microstructural parameters based on bulk alloy composition, thereby demonstrating their usefulness.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs8Na16Al24Si112

NASA Astrophysics Data System (ADS)

Wei, Kaya; Dong, Yongkwan; Nolas, George S.

2016-05-01

A new quaternary clathrate-II composition, Cs8Na16Al24Si112, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs8Na16Al24Si112 were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

Structure and magnetic properties of Co-Ni-Mn alloy coatings (part 2)

NASA Astrophysics Data System (ADS)

Schmidt, V. V.; Zhikhareva, I. G.; Smirnova, N. V.; Shchipanov, V. P.

2018-03-01

Using the method of high-frequency alternating current (HFAC), based on the preliminary model forecasting of the ratio of metal ions in the electrolyte and the phase composition of the coating, Co-Ni-Mn alloy precipitates with the specified magnetic properties are obtained. It is shown that precipitation with a hexagonal close-packed α-Co phase has the highest coercive force. The presence of a free phase in a small amount (2.1 - 2.6% of weight) of Mn increases the ferromagnetic properties of films due to the domain structures with a poorly defecting α-Mn crystal lattice. The adjustable amount of the amorphous Co(OH)2 phase provides the nanostructure dimensions of the crystals.

Phase composition and in vitro bioactivity of porous implants made of bioactive glass S53P4.

PubMed

Fagerlund, S; Massera, J; Moritz, N; Hupa, L; Hupa, M

2012-07-01

This work studied the influence of sintering temperature on the phase composition, compression strength and in vitro properties of implants made of bioactive glass S53P4. The implants were sintered within the temperature range 600-1000°C. Over the whole temperature range studied, consolidation took place mainly via viscous flow sintering, even though there was partial surface crystallization. The mechanical strength of the implants was low but increased with the sintering temperature, from 0.7 MPa at 635°C to 10 MPa at 1000°C. Changes in the composition of simulated body fluid (SBF), the immersion solution, were evaluated by pH measurements and ion analysis using inductively coupled plasma optical emission spectrometry. The development of a calcium phosphate layer on the implant surfaces was verified using scanning electron microscopy-electron-dispersive X-ray analysis. When immersed in SBF, a calcium phosphate layer formed on all the samples, but the structure of this layer was affected by the surface crystalline phases. Hydroxyapatite formed more readily on amorphous and partially crystalline implants containing both primary Na(2)O·CaO·2SiO(2) and secondary Na(2)Ca(4)(PO(4))(2)SiO(4) crystals than on implants containing only primary crystals. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Crystal morphology variation in inkjet-printed organic materials

NASA Astrophysics Data System (ADS)

Ihnen, Andrew C.; Petrock, Anne M.; Chou, Tsengming; Samuels, Phillip J.; Fuchs, Brian E.; Lee, Woo Y.

2011-11-01

The recent commercialization of piezoelectric-based drop-on-demand inkjet printers provides an additive processing platform for producing and micropatterning organic crystal structures. We report an inkjet printing approach where macro- and nano-scale energetic composites composed of cyclotrimethylenetrinitramine (RDX) crystals dispersed in a cellulose acetate butyrate (CAB) matrix are produced by direct phase transformation from organic solvent-based all-liquid inks. The characterization of printed composites illustrates distinct morphological changes dependent on ink deposition parameters. When 10 pL ink droplets rapidly formed a liquid pool, a coffee ring structure containing dendritic RDX crystals was produced. By increasing the substrate temperature, and consequently the evaporation rate of the pooled ink, the coffee ring structure was mitigated and shorter dendrites from up to ∼1 to 0.2 mm with closer arm spacing from ∼15 to 1 μm were produced. When the nucleation and growth of RDX and CAB were confined within the evaporating droplets, a granular structure containing nanoscale RDX crystals was produced. The results suggest that evaporation rate and microfluidic droplet confinement can effectively be used to tailor the morphology of inkjet-printed energetic composites.

Composition and automated crystal orientation mapping of rapid solidification products in hypoeutectic Al-4 at.%Cu alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zweiacker, K. W.; Liu, Can; Gordillo, M. A.

Rmore » apid solidification can produce metastable phases and unusual microstructure modifications in multi-component alloys during additive manufacturing or laser beam welding. Composition and phase mapping by transmission electron microscopy have been used in this paper to characterize the morphologically distinct zones developing in hypoeutectic Al-4 at.% Cu alloy after pulsed laser melting for different crystal growth rate regimes. Deviations of the compositions of the alloy phases from equilibrium predictions and unique orientation relationships between the solidification transformation products have been determined. Specifically, for the columnar growth zone at solidification rates of 0.8 m s - 1 < v < v a = 1.8 m s - 1 , two distinct orientation relationships were established between the concomitantly forming non-equilibrium phases, supersaturated α-Al solid solution and the discontinuously distributed α-Al 2Cu-based θ'-phase, which can be described as {110} θ ∥ {001} α, [001] θ ∥ [110] α and {001} θ ∥ {001} α, [100] θ ∥ [100] α. These orientation relationships permit formation of coherent interphase interfaces with low interfacial free energy. Finally, this endows a kinetic advantage to the thermodynamically less stable θ'-Al 2Cu phase relative to the more stable equilibrium θ-Al 2Cu phase during formation of the morphologically modified eutectic of the columnar growth zone grains, since repeated nucleation is required to establish the discontinuous distribution of θ'-Al 2Cu phase.« less

Composition and automated crystal orientation mapping of rapid solidification products in hypoeutectic Al-4 at.%Cu alloys

DOE PAGES

Zweiacker, K. W.; Liu, Can; Gordillo, M. A.; ...

2017-12-05

Rmore » apid solidification can produce metastable phases and unusual microstructure modifications in multi-component alloys during additive manufacturing or laser beam welding. Composition and phase mapping by transmission electron microscopy have been used in this paper to characterize the morphologically distinct zones developing in hypoeutectic Al-4 at.% Cu alloy after pulsed laser melting for different crystal growth rate regimes. Deviations of the compositions of the alloy phases from equilibrium predictions and unique orientation relationships between the solidification transformation products have been determined. Specifically, for the columnar growth zone at solidification rates of 0.8 m s - 1 < v < v a = 1.8 m s - 1 , two distinct orientation relationships were established between the concomitantly forming non-equilibrium phases, supersaturated α-Al solid solution and the discontinuously distributed α-Al 2Cu-based θ'-phase, which can be described as {110} θ ∥ {001} α, [001] θ ∥ [110] α and {001} θ ∥ {001} α, [100] θ ∥ [100] α. These orientation relationships permit formation of coherent interphase interfaces with low interfacial free energy. Finally, this endows a kinetic advantage to the thermodynamically less stable θ'-Al 2Cu phase relative to the more stable equilibrium θ-Al 2Cu phase during formation of the morphologically modified eutectic of the columnar growth zone grains, since repeated nucleation is required to establish the discontinuous distribution of θ'-Al 2Cu phase.« less

Cosputtering crystal growth of zinc oxide-based composite films: From the effects of doping to phase on photoactivity and gas sensing properties

NASA Astrophysics Data System (ADS)

Liang, Yuan-Chang; Lee, Chia-Min

2016-10-01

ZnO-In2O3 (InO) composite thin films were grown by radio frequency cosputtering ZnO and InO ceramic targets in this study. The indium content of the composite films was varied from 1.7 at. % to 8.2 at. % by varying the InO sputtering power during cosputtering thin-film growth. X-ray diffraction and transmission electron microscopy analysis results show that the high indium content leads to the formation of a separated InO phase in the ZnO matrix. The surface crystallite size and roughness of the ZnO-InO composite films grown here increased with an increasing indium content. Furthermore, under the conditions of a higher indium content and InO sputtering power, the number of crystal defects in the composite films increased, and the optical absorbance edge of the composite films broadened. The photoactivity and ethanol gas sensing response of the ZnO-InO composite films increased as their indium content increased; this finding is highly correlated with the microstructural evolution of ZnO-InO composite films of various indium contents, which is achieved by varying the InO sputtering power during cosputtering.

Crystal structures and infrared spectra of two Fe-bearing hydrous magnesium silicates synthesized at high temperature and pressure

NASA Technical Reports Server (NTRS)

Yang, H.; Prewitt, C. T.; Liu, Z.

2002-01-01

The synthesis and characterization of Fe-bearing phase E and phase E' demonstrate that the phase E-type structures can be rather compliant and complex, and that as we further explore the temperature-pressure-composition space, other types of structures that are similar to or related to the structure of phase E may be discovered.

Crystallization of Ca-Al-Rich Inclusions: Experimental Studies on the Effects of Repeated Heating Events

NASA Technical Reports Server (NTRS)

Paque, Julie M.; Lofgren, Gary E.; Le, Loan

2000-01-01

The observed textures and chemistry of Ca-Al-rich inclusions (CAIs) are presumed to be the culmination of a series of repeated heating and cooling events in the early history of the solar nebula. We have examined the effects of these heating/cooling cycles experimentally on a bulk composition representing an average Type B Ca-Al-rich inclusion composition. We have tested the effect of the nature of the starting material. Although the most recent and/or highest temperature event prior to incorporation into the parent body dominates the texture and chemistry of the CAI, prior events also affect the phase compositions and textures. We have determined that heating precursor grains to about 1275 C prior to the final melting event increases the likelihood of anorthite crystallization in subsequent higher temperature events and a prior high temperature even that produced dendritic melilite results in melilite that shows evidence of rapid crystallization in subsequent lower temperature events. Prior low temperature pre-crystallization events produce final ran products with pyroxene compositions similar to Type B Ca-Al-rich inclusions, and the glass (residual liquid) composition is more anorthitic than any other experiments to date. The addition of Pt powder to the starting material appears to enhance the ability of anorthite to nucleate from this composition.

The crystal structure and morphology of NiO-YSZ composite that prepared from local zircon concentrate of Bangka Island

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahmawati, F., E-mail: fitria@mipa.uns.ac.id; Apriyani, K.; Heraldy, E.

2016-03-29

In order to increase the economic value of local zircon concentrate from Bangka Island, NiO-YSZ was synthesized from Zirconia, ZrO{sub 2} that was prepared from local zircon concentrate. The NiO-YSZ composite was synthesized by solid state reaction method. XRD analysis equipped with Le Bail refinement was carried out to analyze the crystal structure and cell parameters of the prepared materials. The result showed that zirconia was crystallized in tetragonal structure with a space group of P42/NMC. Yttria-Stabilized-Zirconia (YSZ) was prepared by doping 8% mol yttrium oxide into zirconia and then sintered at 1250°C for 3 hours. Doping of 8% molmore » Yttria allowed phase transformation of zirconia from tetragonal into the cubic structure. Meanwhile, the composite of NiO-YSZ consists of two crystalline phases, i.e. the NiO with cubic structure and the YSZ with cubic structure. SEM analysis of the prepared materials shows that the addition of NiO into YSZ allows the morphology to become more roughness with larger grain size.« less

Investigation of the Nd-rich phases in the Nd-Fe-B system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, W.; Zhou, S.; Wang, R.

1988-11-15

The crystal structures and the compositions of the Nd-rich phases in the Nd-Fe-B system have been investigated by means of transmission electron microscopy, x-ray diffraction, and Auger spectroscopy techniques. It has been observed that there are two kinds of Nd-rich phases with different structures and compositions. Most of the Nd-rich phases will undergo a phase transformation when the powder is sintered at high temperatures. This phase transformation is accompanied by the introduction of oxygen into the alloy which will change from a ternary system into a quaternary one. Both of the two Nd-rich phases are stable phases in this latermore » system. With the aid of the EDX and the Auger spectroscope, the compositions of the dhcp and the fcc Nd-rich phases have been determined. The Nd contents of the two phases are about 90 and 70 at. %, respectively, with the later phase containing about 15 at. % of oxygen.« less

The Lunar Magma Ocean: Sharpening the Focus on Process and Composition

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Draper, D. S.

2014-01-01

The currently accepted model for the formation of the lunar anorthositic crust is by flotation from a crystallizing lunar magma ocean (LMO) shortly following lunar accretion. Anorthositic crust is globally distributed and old, whereas the mare basalts are younger and derived from a source region that has experienced plagioclase extraction. Several attempts at modelling such a crystallization sequence have been made [e.g. 1, 2], but our ever-increasing knowledge of the lunar samples and surface have raised as many questions as these models have answered. This abstract presents results from our ongoing ex-periments simulating LMO crystallization and address-ing a range of variables. We investigate two bulk com-positions, which span most of the range of suggested lunar bulk compositions, from the refractory element enriched Taylor Whole Moon (TWM) [3] to the more Earth-like Lunar Primitive Upper Mantle (LPUM) [4]. We also investigate two potential crystallization mod-els: Fully fractional, where crystallizing phases are separated from the magma as they form and sink (or float in the case of plagioclase) throughout magma ocean solidification; and a two-step process suggested by [1, 5] with an initial stage of equilibrium crystalliza-tion, where crystals remain entrained in the magma before the crystal burden increases viscosity enough that convection slows and the crystals settle, followed by fractional crystallization. Here we consider the frac-tional crystallization part of this process; the equilibri-um cumulates having been determined by [6].

The evolution of young silicic lavas at Medicine Lake Volcano, California: Implications for the origin of compositional gaps in calc-alkaline series lavas

USGS Publications Warehouse

Grove, T.L.; Donnelly-Nolan, J. M.

1986-01-01

At Medicine Lake Volcano, California, the compositional gap between andesite (57-62 wt.% SiO2) and rhyolite (73-74 wt.% SiO2) has been generated by fractional crystallization. Assimilation of silicic crust has also occurred along with fractionation. Two varieties of inclusions found in Holocene rhyolite flows, hornblende gabbros and aphyric andesites, provide information on the crystallization path followed by lavas parental to the rhyolite. The hornblende gabbros are magmatic cumulate residues and their mineral assemblages are preserved evidence of the phases that crystallized from an andesitic precursor lava to generate the rhyolite lavas. The andesitic inclusions represent samples of a parental andesite and record the early part of the differentiation history. Olivine, plagioclase and augite crystallization begins the differentiation history, followed by the disappearance of olivine and augite through reaction with the liquid to form orthopyroxene and amphibole. Further crystallization of the assemblage plagioclase, amphibole, orthopyroxene, magnetite, and apatite from a high-SiO2 andesite leads to rhyolite. This final crystallization process occurs on a cotectic that is nearly horizontal in temperature-composition space. Since a large amount of crystallization occurs over a limited temperature interval, a compositional gap develops between rhyolite and high SiO2 andesite. Liquidus surfaces with shallow slopes in temperature-composition space are characteristic of several late-stage crystallization assemblages in the andesite to rhyolite compositional range. Experimentally produced plagioclase+ amphibole+orthopyroxene+magnetite and plagioclase+ augite+low-Ca pyroxene+magnetite cotectics have liquidus slopes that are nearly flat. At other calc-alkaline volcanic centers crystallization processes involving large compositional changes over small temperature intervals may also be important in the development of bimodal volcanism (i.e. the existence of a composition gap). At Mt. Mazama and Mt. St. Helens, USA and Aso Caldera and Shikotsu, Japan the amphibole-bearing assemblage was important. At Krakatau, Indonesia and Katmai, USA, an augite+orthopyroxene-bearing assemblage was important. In addition to its role in the production of a compositional gap between intermediate and rhyolitic lavas, the crystallization process increases the H2O content of the residual liquid. This rapid increase in residual liquid volatile content which results from the precipitation of a large proportion of crystalline solids may be an important factor among several that lead to explosive silicic eruptions. ?? 1986 Springer-Verlag.

A comparative study of monoclonal antibodies. 1. Phase behavior and protein-protein interactions

PubMed Central

Lewus, Rachael A.; Levy, Nicholas E.; Lenhoff, Abraham M.; Sandler, Stanley I.

2018-01-01

Protein phase behavior is involved in numerous aspects of downstream processing, either by design as in crystallization or precipitation processes, or as an undesired effect, such as aggregation. This work explores the phase behavior of eight monoclonal antibodies (mAbs) that exhibit liquid-liquid separation, aggregation, gelation, and crystallization. The phase behavior has been studied systematically as a function of a number of factors, including solution composition and pH, in order to explore the degree of variability among different antibodies. Comparisons of the locations of phase boundaries show consistent trends as a function of solution composition; however, changing the solution pH has different effects on each of the antibodies studied. Furthermore, the types of dense phases formed varied among the antibodies. Protein-protein interactions, as reflected by values of the osmotic second virial coefficient, are used to correlate the phase behavior. The primary findings are that values of the osmotic second virial coefficient are useful for correlating phase boundary locations, though there is appreciable variability among the antibodies in the apparent strengths of the intrinsic protein-protein attraction manifested. However, the osmotic second virial coefficient does not provide a clear basis to predict the type of dense phase likely to result under a given set of solution conditions. PMID:25378269

Reversible amorphous-crystalline phase changes in a wide range of Se1-xTex alloys studied using ultrafast differential scanning calorimetry

NASA Astrophysics Data System (ADS)

Vermeulen, Paul. A.; Momand, Jamo; Kooi, Bart J.

2014-07-01

The reversible amorphous-crystalline phase change in a chalcogenide material, specifically the Se1-xTex alloy, has been investigated for the first time using ultrafast differential scanning calorimetry. Heating rates and cooling rates up to 5000 K/s were used. Repeated reversible amorphous-crystalline phase switching was achieved by consecutively melting, melt-quenching, and recrystallizing upon heating. Using a well-conditioned method, the composition of a single sample was allowed to shift slowly from 15 at. %Te to 60 at. %Te, eliminating sample-to-sample variability from the measurements. Using Energy Dispersive X-ray Spectroscopy composition analysis, the onset of melting for different Te-concentrations was confirmed to coincide with the literature solidus line, validating the use of the onset of melting Tm as a composition indicator. The glass transition Tg and crystallization temperature Tc could be determined accurately, allowing the construction of extended phase diagrams. It was found that Tm and Tg increase (but Tg/Tm decrease slightly) with increasing Te-concentration. Contrarily, the Tc decreases substantially, indicating that the amorphous phase becomes progressively unfavorable. This coincides well with the observation that the critical quench rate to prevent crystallization increases about three orders of magnitude with increasing Te concentration. Due to the employment of a large range of heating rates, non-Arrhenius behavior was detected, indicating that the undercooled liquid SeTe is a fragile liquid. The activation energy of crystallization was found to increase 0.5-0.6 eV when the Te concentration increases from 15 to 30 at. % Te, but it ceases to increase when approaching 50 at. % Te.

The composite structure of mixed τ-(Ag, Cu)xV2O5 bronzes—Evidence for T dependant guest-species ordering and mobility

NASA Astrophysics Data System (ADS)

Hermes, Wilfred; Dollé, Mickaël; Rozier, Patrick; Lidin, Sven

2013-03-01

The complex structural behavior of τ-[AgCu]˜0.92V4O10 has been elucidated by single crystal X-ray diffraction and thermal analysis. The τ-phase region is apparently composed of several distinct phases and this study identifies at least three: τ1rt, τ2rt and τlt. τ1rt and τ2rt have slightly different compositions and crystal habits. Both phases transform to τlt at low temperature. The room temperature modification τ1rt crystallizes in an incommensurately modulated structure with monoclinic symmetry C2(0β1/2) [equivalent to no 5.4, B2(01/2γ) in the Intnl. Tables for Crystallography, Volume C] and the cell parameters a=11.757(4) Å, b=3.6942(5) Å c=9.463(2) Å β=114.62(2)° and the q-vector (0 0.92 1/2), but it is more convenient to transform this to a setting with a non-standard centering X=(1/2 1/2 0 0; 0 0 1/2 1/2; 1/2 1/2 1/2 1/2;) and an axial q vector (0 0.92 0). The structure features a vanadate host lattice with Cu and Ag guests forming an incommensurate composite. The structural data indicates perfect Ag/Cu ordering. At low temperature this modification is replaced by a triclinic phase characterized by two independent q-vectors. The τ2rt phase is similar to the low temperature modification τlt but the satellite reflections are generally more diffuse.

Advanced methods for preparation and characterization of infrared detector materials. [crystallization and phase diagrams of Hg sub 1-x Cd sub x Te

NASA Technical Reports Server (NTRS)

Lehoczy, S. L.

1979-01-01

Crystal growth of Hg sub 1-x Cd sub x Te and density measurements of ingot slices are discussed. Radial compositional variations are evaluated from the results of infrared transmission edge mapping. The pseudo-binary HgTe-CdTe phase diagram is examined with reference to differential thermal analysis measurements. The phase equilibria calculations, based on the 'regular association solution' theory (R.A.S.) are explained and, using the obtained R.A.S. parameters, the activities of Hg, Cd, and Te vapors and their partial pressures over the pseudo-binary melt are calculated.

Reverse-mode thermoresponsive light attenuators produced by optical anisotropic composites of nematic liquid crystals and reactive mesogens

NASA Astrophysics Data System (ADS)

Kakiuchida, Hiroshi; Ogiwara, Akifumi

2018-04-01

Polymer network liquid crystals (PNLCs) whose optical transmittance state switches between transparence at low temperatures and haze at high temperatures were fabricated from mixtures of nematic liquid crystals (LCs) and reactive mesogens (RMs). This PNLC structure is simple but effective, namely, consists of micro-scale domains of orientation-ordered LCs and anisotropically polymerized RMs. The domains form through photopolymerization induced phase separation with inhomogeneous irradiation projected by laser speckling techniques. This irradiation method enables you to control the size and shape of phase-separation domains, and these PNLCs can be applied to novel thermoresponsive optical devices; optical isolators, thermometric sheets, and smart windows.

Vitrification of copper flotation waste.

PubMed

Karamanov, Alexander; Aloisi, Mirko; Pelino, Mario

2007-02-09

The vitrification of an hazardous iron-rich waste (W), arising from slag flotation of copper production, was studied. Two glasses, containing 30wt% W were melted for 30min at 1400 degrees C. The first batch, labeled WSZ, was obtained by mixing W, blast furnace slag (S) and zeolite tuff (Z), whereas the second, labeled WG, was prepared by mixing W, glass cullet (G), sand and limestone. The glass frits showed high chemical durability, measured by the TCLP test. The crystallization of the glasses was evaluated by DTA. The crystal phases formed were identified by XRD resulting to be pyroxene and wollastonite solid solutions, magnetite and hematite. The morphology of the glass-ceramics was observed by optical and scanning electron microscopy. WSZ composition showed a high rate of bulk crystallization and resulted to be suitable for producing glass-ceramics by a short crystallization heat-treatment. WG composition showed a low crystallization rate and good sinterability; glass-ceramics were obtained by sinter-crystallization of the glass frit.

Structural, mechanical, and magnetic properties of ferrite-austenite mixture in evaporated 304 stainless steel thin films

NASA Astrophysics Data System (ADS)

Merakeb, Noureddine; Messai, Amel; Djelloul, Abdelkader; Ayesh, Ahmad I.

2015-11-01

In this paper, we investigate the structure, composition, magnetic, and mechanical properties of stainless steel thin films formed by thermal evaporation technique. These thin films reveal novel structural and physical properties where they were found to consist of nanocrystals that are ~90 % body-centred cubic crystal structure which holds ferromagnetic properties (α-phase), and ~10 % face-centred cubic crystal structure which is paramagnetic at room temperature (γ-phase). The presence of the above phases was quantified by X-ray diffraction, transmission electron microscopy, and conversion electron Mössbauer spectroscopy. The magnetic properties were evaluated by a superconducting quantum interference device magnetometer, and they confirmed the dual-phase crystal structure of the stainless thin films, where the presence of γ-phase reduced the magnetization of the produced thin films. In addition, the fabricated stainless steel thin films did not contain micro-cracks, and they exhibit a tensile stress of about 1.7 GPa, hardness of 7.5 GPa, and elastic modulus of 104 GPa.

Thermal collapse and hierarchy of polymorphs in a faujasite-type zeolite and its analogous melt-quenched glass

NASA Astrophysics Data System (ADS)

Palenta, Theresia; Fuhrmann, Sindy; Greaves, G. Neville; Schwieger, Wilhelm; Wondraczek, Lothar

2015-02-01

We examine the route of structural collapse and re-crystallization of faujasite-type (Na,K)-LSX zeolite. As the first step, a rather stable amorphous high density phase HDAcollapse is generated through an order-disorder transition from the original zeolite via a low density phase LDAcollapse, at around 790 °C. We find that the overall amorphization is driven by an increase in the bond angle distribution within T-O-T and a change in ring statistics to 6-membered TO4 (T = Si4+, Al3+) rings at the expense of 4-membered rings. The HDAamorph transforms into crystalline nepheline, though, through an intermediate metastable carnegieite phase. In comparison, the melt-derived glass of similar composition, HDAMQ, crystallizes directly into the nepheline phase without the occurrence of intermediate carnegieite. This is attributed to the higher structural order of the faujasite-derived HDAcollapse which prefers the re-crystallization into the highly symmetric carnegieite phase before transformation into nepheline with lower symmetry.

Identification and characterization of the intermediate phase in hybrid organic-inorganic MAPbI3 perovskite.

PubMed

Guo, Xin; McCleese, Christopher; Kolodziej, Charles; Samia, Anna C S; Zhao, Yixin; Burda, Clemens

2016-03-07

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

Phase transformations, anisotropic pyroelectric energy harvesting and electrocaloric properties of (Pb,La)(Zr,Sn,Ti)O3 single crystals.

PubMed

Zhuo, Fangping; Li, Qiang; Gao, Jinghan; Yan, Qingfeng; Zhang, Yiling; Xi, Xiaoqing; Chu, Xiangcheng

2017-05-31

(Pb,La)(Zr,Sn,Ti)O 3 (PLZST) single crystals with their chemical composition located at the tetragonal antiferroelectric region are grown via the flux method in a PbO-PbF 2 -B 2 O 3 mixture. Segregation of the Ti 4+ component in the as-grown crystals is observed due to the strong affinity between the oxygen anion and Ti 4+ ions. The critical electric field of the antiferroelectric to ferroelectric phase transition is determined to be about 0.5 kV mm -1 . The electric field induced ferroelectric phase transforms back into the antiferroelectric phase at a depolarization temperature of 125 °C. Anisotropy of the harvested energy density and electrocaloric behaviors are achieved for the [100], [110] and [111]-oriented PLZST crystals. Based on the thermodynamic theory approach, all the abovementioned behaviors originate from the anisotropic total entropy change. Enhanced electrocaloric strength (0.3 K mm kV -1 ) and the harvested energy density of 0.62 J cm -3 are obtained in the [111]-oriented PLZST crystals. Our results demonstrate the competence of PLZST single crystals for cooling devices and pyroelectric energy harvesting and provide new opportunities to improve energy harvesting density and electrocaloric properties via the anisotropic structural layout, which make the PLZST crystals attractive for solid state cooling devices and energy conversion technologies.

Microfluidic Droplet Dehydration for Concentrating Processes in Biomolecules

NASA Astrophysics Data System (ADS)

Anna, Shelley

2014-03-01

Droplets in microfluidic devices have proven useful as picoliter reactors for biochemical processing operations such as polymerase chain reaction, protein crystallization, and the study of enzyme kinetics. Although droplets are typically considered to be self-contained, constant volume reactors, there can be significant transport between the dispersed and continuous phases depending on solubility and other factors. In the present talk, we show that water droplets trapped within a microfluidic device for tens of hours slowly dehydrate, concentrating the contents encapsulated within. We use this slow dehydration along with control of the initial droplet composition to influence gellation, crystallization, and phase separation processes. By examining these concentrating processes in many trapped drops at once we gain insight into the stochastic nature of the events. In one example, we show that dehydration rate impacts the probability of forming a specific crystal habit in a crystallizing amino acid. In another example, we phase separate a common aqueous two-phase system within droplets and use the ensuing two phases to separate DNA from an initial mixture. We further influence wetting conditions between the two aqueous polymer phases and the continuous oil, promoting complete de-wetting and physical separation of the polymer phases. Thus, controlled dehydration of droplets allows for concentration, separation, and purification of important biomolecules on a chip.

Melt growth of zinc aluminate spinel single crystal by the micro-pulling down method under atmospheric pressure

NASA Astrophysics Data System (ADS)

Kamada, K.; Shoji, Y.; Yamaji, A.; Kurosawa, S.; Yokota, Yuui; Ohashi, Y.; Kim, Kyoung Jin; Ivanov, M.; Kochurikhin, V. V.; Yoshikawa, A.

2018-06-01

ZnAl2O4 crystals were grown using few starting compositions with various ZnO:AlO3/2 ratio using an Ir wire seed and Ir + Re crucible under ordinary pressure with Ar + 2%O2 atmosphere by the radiofrequency heating μ-PD furnace. The ZnAl2O4 spinel single crystal with 4 mm diameter could be successfully grown by the μ-PD method by optimization of starting melt composition considering with Zinc oxide evaporation. During 10 min of growth under normal pressure the formation of ZnAl2O4 single phase observed even at high vapor pressure of ZnO. The transmittance spectra and X-ray locking curve were measured for evaluating of grown ZnAl2O4 crystals quality.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Righettoni, Marco; Pratsinis, Sotiris E., E-mail: sotiris.pratsinis@ptl.mavt.ethz.ch

Highlights: • Flame-made WO{sub 3} nanoparticles with closely controlled crystal and grain size. • Dynamic phase transition of annealing of pure and Si-doped WO{sub 3} by in situ XRD. • Irreversible evolution of WO{sub 3} crystallinity by heating/cooling during its annealing. • Si-doping alters the WO{sub 3} crystallinity dynamics and stabilizes nanosized WO{sub 3}. • Flame-made nano-WO{sub 3} can sense NO at the ppb level. - Abstract: Tungsten trioxide is a semiconductor with distinct applications in gas sensors, catalysis, batteries and pigments. As such the transition between its different crystal structures during its annealing are of interest, especially for sensormore » applications. Here, WO{sub 3} nanoparticles with closely controlled crystal and grain size (9–15 nm) and phase composition are made by flame spray pyrolysis and the formation of different WO{sub 3} phases during annealing is investigated. Most notably, the dynamic phase transition and crystal size evolution of WO{sub 3} during heating and cooling is monitored by in situ X-ray diffraction revealing how metastable WO{sub 3} phases can be captured stably. The effect of Si-doping is studied since it is used in practise to control crystal growth and phase transition during metal oxide synthesis and processing. Finally the influence of annealing on the WO{sub 3} sensing performance of NO, a lung inflammation tracer in the human breath, is explored at the ppb-level.« less

Influence of surfactant on the thermal behavior of marigold oil emulsions with liquid crystal phases.

PubMed

dos Santos, Orlando David Henrique; da Rocha-Filho, Pedro Alves

2007-05-01

Vegetable oils have been largely consumed owing to the interest of pharmaceutical and cosmetic industries in using natural raw materials. The production of stable emulsions with vegetable oils challenges formulators due to its variability in composition and fatty acids constitution within batches produced. In the present work, it was studied that the influence of the size of carbon chain and the number of ethylene oxide moieties of the surfactant on the thermal behavior of eight emulsions prepared with marigold oil stabilized by liquid crystal phases. Differential scanning calorimetry (DSC) was used to determine the thermal behavior of the emulsions. The ratio of bound water was calculated, being between 29.0 and 42.0%, confirming the extension of the liquid-crystalline net in the external phase. Changing the lipophilic surfactant from Ceteth-2 to Steareth-2, there was an increase in the temperature of phase transition of the liquid crystal influencing the system stability. Calorimetric study is very useful in understanding the performance of liquid crystals with the increase of temperature and to estimate emulsions stability.

Magneto-transport properties of Co3O4 nanoparticles added (Cu0.5Tl0.5)Ba2Ca2Cu3O10-δ superconducting phase

NASA Astrophysics Data System (ADS)

Mumtaz, M.; Baig, Mirza Hassan; Waqee-ur-Rehman, M.; Nasir Khan, M.

2018-05-01

Solid-state reaction method was used to synthesize Cu0.5Tl0.5Ba2Ca2Cu3O10-δ (CuTl-1223) superconducting phase and sol-gel method was used to prepare cobalt oxide (Co3O4) magnetic nanoparticles. These Co3O4 nanoparticles were added in CuTl-1223 superconducting matrix to get (Co3O4)x/CuTl-1223; x = 0-2.00 wt.% nanoparticles-superconductor composites. The effects of Co3O4 nanoparticles on crystal structure, phase formation, phase purity and infield superconducting transport properties of CuTl-1223 phase were investigated at different operating temperatures and external applied magnetic fields. The crystal structure and phase formation of Co3O4 nanoparticles and CuTl-1223 superconductor were determined by X-ray diffraction (XRD) technique. XRD peaks of Co3O4 nanoparticles were well indexed according to FCC crystal structure and the average particle size of 70 nm was calculated by using Debye-Scherer's formula. The unaltered crystal structure of host CuTl-1223 superconducting phase (i.e. Tetragonal) with the addition of Co3O4 nanoparticles indicated the dispersion of nanoparticles at inter-granular sites. Temperature dependent magneto-transport superconducting properties of (Co3O4)x/CuTl-1223 composites were investigated by zero field cooled (ZFC) and field cooled (FC) magnetic moment versus temperature (M-T) measurements. The onset transition temperatures {TcOnset (K)} was decreased along with the suppression of diamagnetic amplitude of CuTl-1223 superconducting phase with the addition of magnetic Co3O4 nanoparticles. Temperature dependent magnetic hysteresis (M-H loops) measurements of (Co3O4)x/CuTl-1223 composites were carried out at different operating temperatures from 5 K to 150 K. Critical current density (Jc) was calculated from M-H loops measurements by using Bean's model. Like the suppression of TcOnset (K) values, Jc was also decreased with the inclusion of Co3O4 nanoparticles. It was also observed that variation of Jc with H followed the power law Jc = βH-α at low operating temperatures 5 K and 20 K only.

Single particle measurements of the chemical composition of cirrus ice residue during CRYSTAL-FACE

NASA Astrophysics Data System (ADS)

Cziczo, D. J.; Murphy, D. M.; Hudson, P. K.; Thomson, D. S.

2004-02-01

The first real-time, in situ, investigation of the chemical composition of the residue of cirrus ice crystals was performed during July 2002. This study was undertaken on a NASA WB-57F high-altitude research aircraft as part of CRYSTAL-FACE, a field campaign which sought to further our understanding of the relation of clouds, water vapor, and climate by characterizing, among other parameters, anvil cirrus formed about the Florida peninsula. A counter flow virtual impactor (CVI) was used to separate cirrus ice from the unactivated interstitial aerosol particles and evaporate condensed-phase water. Residual material, on a crystal-by-crystal basis, was subsequently analyzed using the NOAA Aeronomy Laboratory's Particle Analysis by Laser Mass Spectrometry (PALMS) instrument. Sampling was performed from 5 to 15 km altitude and from 12° to 28° north latitude within cirrus originating over land and ocean. Chemical composition measurements provided several important results. Sea salt was often incorporated into cirrus, consistent with homogeneous ice formation by aerosol particles from the marine boundary layer. Size measurements showed that large particles preferentially froze over smaller ones. Meteoritic material was found within ice crystals, indicative of a relation between stratospheric aerosol particles and tropospheric clouds. Mineral dust was the dominant residue observed in clouds formed during a dust transport event from the Sahara, consistent with a heterogeneous freezing mechanism. These results show that chemical composition and size are important determinants of which aerosol particles form cirrus ice crystals.

Automated Phase Segmentation for Large-Scale X-ray Diffraction Data Using a Graph-Based Phase Segmentation (GPhase) Algorithm.

PubMed

Xiong, Zheng; He, Yinyan; Hattrick-Simpers, Jason R; Hu, Jianjun

2017-03-13

The creation of composition-processing-structure relationships currently represents a key bottleneck for data analysis for high-throughput experimental (HTE) material studies. Here we propose an automated phase diagram attribution algorithm for HTE data analysis that uses a graph-based segmentation algorithm and Delaunay tessellation to create a crystal phase diagram from high throughput libraries of X-ray diffraction (XRD) patterns. We also propose the sample-pair based objective evaluation measures for the phase diagram prediction problem. Our approach was validated using 278 diffraction patterns from a Fe-Ga-Pd composition spread sample with a prediction precision of 0.934 and a Matthews Correlation Coefficient score of 0.823. The algorithm was then applied to the open Ni-Mn-Al thin-film composition spread sample to obtain the first predicted phase diagram mapping for that sample.

Structure and magnetic properties of flux grown single crystals of Co3-xFexSn2S2 shandites

NASA Astrophysics Data System (ADS)

Kassem, Mohamed A.; Tabata, Yoshikazu; Waki, Takeshi; Nakamura, Hiroyuki

2016-01-01

We report a successful single crystal growth of the shandite-type half-metallic ferromagnet Co3Sn2S2, and its Fe-substituted compounds, Co3-xFexSn2S2, by employing the flux method. Although Fe3Sn2S2 is unstable phase, we found that using the self Sn flux enables us to obtain single phase crystals up to x=0.53. The chemical composition of the grown plate-shaped single crystals was examined using wavelength-dispersive X-ray spectroscopy. The shandite structure with R 3 ̅m symmetry was confirmed by powder X-ray diffraction and the crystal structure parameters were refined using the Rietveld method. Magnetization measurements show suppression of the ferromagnetic order upon Fe-substitution , as well as in other substituted systems such as In- and Ni-substituted Co3Sn2S2. The almost identical magnetic phase diagrams of the Fe- and In-substituted compounds indicate that the electron number is dominantly significant to the magnetism in the Co-based shandite.

Investigation of the Microstructure and Mechanical Properties of Copper-Graphite Composites Reinforced with Single-Crystal α-Al₂O₃ Fibres by Hot Isostatic Pressing.

PubMed

Zhang, Guihang; Jiang, Xiaosong; Qiao, ChangJun; Shao, Zhenyi; Zhu, Degui; Zhu, Minhao; Valcarcel, Victor

2018-06-11

Single-crystal α-Al₂O₃ fibres can be utilized as a novel reinforcement in high-temperature composites owing to their high elastic modulus, chemical and thermal stability. Unlike non-oxide fibres and polycrystalline alumina fibres, high-temperature oxidation and polycrystalline particles boundary growth will not occur for single-crystal α-Al₂O₃ fibres. In this work, single-crystal α-Al₂O₃ whiskers and Al₂O₃ particles synergistic reinforced copper-graphite composites were fabricated by mechanical alloying and hot isostatic pressing techniques. The phase compositions, microstructures, and fracture morphologies of the composites were investigated using X-ray diffraction, a scanning electron microscope equipped with an X-ray energy-dispersive spectrometer (EDS), an electron probe microscopic analysis equipped with wavelength-dispersive spectrometer, and a transmission electron microscope equipped with EDS. The mechanical properties have been measured by a micro-hardness tester and electronic universal testing machine. The results show that the reinforcements were unevenly distributed in the matrix with the increase of their content and there were some micro-cracks located at the interface between the reinforcement and the matrix. With the increase of the Al₂O₃ whisker content, the compressive strength of the composites first increased and then decreased, while the hardness decreased. The fracture and strengthening mechanisms of the composite materials were explored on the basis of the structure and composition of the composites through the formation and function of the interface. The main strengthening mechanism in the composites was fine grain strengthening and solid solution strengthening. The fracture type of the composites was brittle fracture.

The effect of crystal structure of TiO2 nanotubes on the formation of calcium phosphate coatings during biomimetic deposition

NASA Astrophysics Data System (ADS)

Liu, Yi; Kim, Sun; McLeod, John A.; Li, Jun; Guo, Xiaoxuan; Sham, Tsun-Kong; Liu, Lijia

2017-02-01

The crystallization process of bioactive calcium phosphate (CaP) species via biomimetic deposition onto anodic TiO2 nanotubes is investigated. The porous surface of nanostructured TiO2 provides an ideal substrate for CaP crystallization. The compositions of CaP coatings are studied using X-ray absorption near-edge structures (XANES) at the Ca K-edge. Using detection modes with different probing depths, both the surface of the CaP coating and the CaP-TiO2 interface are simultaneously analyzed. Calcium phosphate (CaP) species, such as hydroxyapatite (HAp), octacalcium phosphate (Ca8(HPO4)2(PO4)4·5H2O, OCP), brushite (CaHPO4·2H2O, DCPD), and amorphous calcium phosphate (ACP), are found in the CaP coatings. TiO2 nanotubes of amorphous and anatase phases are comparatively studied to determine their effect on the efficiency of CaP formation and the phase transformation among CaP species in prolonged deposition time. It is found the composition of CaP coating has a strong dependency on the crystal structure of TiO2 substrate and the kinetics (deposition time).

Dielectric and Energy Storage Properties of the Heterogeneous P(VDF-HFP)/PC Composite Films

NASA Astrophysics Data System (ADS)

Zhao, Xiaojia; Peng, Guirong; Zhan, Zaiji

2017-12-01

Polymer-based materials with a high discharge energy and low energy loss have attracted considerable attention for energy storage applications. A new class of polymer-based composite films composed of amorphous polycarbonate (PC) and poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)] has been fabricated by simply solution blending followed by thermal treatment under vacuum. The results show that the diameter of the spherical phase for PC and the melting temperature of P(VDF-HFP) increase, and the crystallinity and crystallization temperature of P(VDF-HFP) decrease with increasing PC content. The phase transition from the polar β phase to weak polarity γ phase is induced by PC addition. Moreover, the Curie temperature of the P(VDF-HFP)/PC composite films shifts to a lower temperature. With the addition of PC, the permittivity, polarization and discharge energy of the P(VDF-HFP)/PC composite films slightly decrease. However, the energy loss is significantly reduced.

Oxygen production by electrolysis of molten lunar regolith

NASA Technical Reports Server (NTRS)

Haskin, Larry A.

1990-01-01

The goal of this study was threefold. First, the theoretical energy requirements of the process were to be defined. This includes studies of the relevant oxidation-reduction reactions in the melt, their kinetics and energies of reaction, and experimental determination of production efficiencies and melt resistivities as functions of melt composition and applied potential. Second, the product(s) of silicate electrolysis were to be characterized. This includes: (1) evaluating the phase relationships in the systems SiO2-TiO2-Al2O3-MgO-FeO-CaO and Fe-Si; (2) estimating the compositions of the metal products as a function of applied potential and feedstock composition based on phase equilibria in the Fe-Si system and free energy values for SiO2 and FeO reported in the literature; (3) definition of compositions of products in actual experiments; and (4) definition of the form the product takes (whether phases separate or remain fixed, whether crystals settle or float in the remaining melt, and how large crystals form). Third, materials for these highly corrosive high-temperature silicate melts were to be identified. This includes identifing materials that may be either inert or thermodynamically stable in these melts, and experimental testing of the materials to confirm that they do not deteriorate. The results are discussed within this framework.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Huidong; Deng, Zhiqun; Carlson, Thomas J.

Piezoelectric materials have been used in underwater acoustic transducers for nearly a century. In this paper, we reviewed four different types of piezoelectric materials: piezoelectric ceramics, single crystals, composites, and polymers, which are widely used in underwater acoustic transducers nowadays. Piezoelectric ceramics are the most dominant material type and are used as a single-phase material or one of the end members in composites. Piezoelectric single crystals offer outstanding electromechanical response but are limited by their manufacturing cost. Piezoelectric polymers provide excellent acoustic impedance matching and transducer fabrication flexibility although their piezoelectric properties are not as good as ceramics and singlemore » crystals. Composites combined the merits of ceramics and polymers and are receiving increased attention. The typical structure and electromechanical properties of each type of materials are introduced and discussed with respect to underwater acoustic transducer applications. Their advantages and disadvantages are summarized. Some of the critical design considerations when developing underwater acoustic transducers with these materials are also touched upon.« less

One-, two- and three-phase viscosity treatments for basaltic lava flows

PubMed Central

Harris, Andrew J. L.; Allen, John S.

2009-01-01

Lava flows comprise three-phase mixtures of melt, crystals, and bubbles. While existing one-phase treatments allow melt phase viscosity to be assessed on the basis of composition, water content, and/or temperature, two-phase treatments constrain the effects of crystallinity or vesicularity on mixture viscosity. However, three-phase treatments, allowing for the effects of coexisting crystallinity and vesicularity, are not well understood. We investigate existing one- and two-phase treatments using lava flow case studies from Mauna Loa (Hawaii) and Mount Etna (Italy) and compare these with a three-phase treatment that has not been applied previously to basaltic mixtures. At Etna, melt viscosities of 425 ± 30 Pa s are expected for well-degassed (0.1 w. % H2O), and 135 ± 10 Pa s for less well-degassed (0.4 wt % H2O), melt at 1080°C. Application of a three-phase model yields mixture viscosities (45% crystals, 25–35% vesicles) in the range 5600–12,500 Pa s. This compares with a measured value for Etnean lava of 9400 ± 1500 Pa s. At Mauna Loa, the three-phase treatment provides a fit with the full range of field measured viscosities, giving three-phase mixture viscosities, upon eruption, of 110–140 Pa s (5% crystals, no bubble effect due to sheared vesicles) to 850–1400 Pa s (25–30% crystals, 40–60% spherical vesicles). The ability of the three-phase treatment to characterize the full range of melt-crystal-bubble mixture viscosities in both settings indicates the potential of this method in characterizing basaltic lava mixture viscosity. PMID:21691456

Features of structure formation in the low modulus quasi-single crystal from Zr-25%Nb alloy at cold rolling

NASA Astrophysics Data System (ADS)

Isaenkova, M.; Perlovich, Yu.; Fesenko, V.; Babich, Y.; Zaripova, M.; Krapivka, N.

2018-05-01

The paper presents the results of investigation of the regularities of the structure and texture formation during rolling of single crystals of Zr-25%Nb alloy differing in their initial orientations relative to the external principal directions in the rolled plate: normal (ND) and rolling directions (RD). The features of rolled single crystals with initial orientations of planes {001}, {011} or {111} parallel to the rolling plane and different crystallographic directions along RD are considered. A comparison of the peculiarities of plastic deformation in a polycrystalline alloy of the same composition is made. For the samples studied, a decrease in the lattice parameter of the β-phase has been recorded, the minimum of the parameter being observed for different degrees of deformation, varying from 20 to 50%. Observed decrease in the unit cell parameter can be connected with the precipitation of the α(α')-Zr phase from the deformed nonequilibrium β-phase of the Zr-25%Nb alloy, i.e. change in the composition of the solid solution. Distributions of the increase in the dimensions of the deformed single crystal along RD and the transverse direction (TD) with its deformation up to 30% in thickness, which indicate the anisotropy of the plasticity of single crystals during their rolling, are constructed on stereographic projection. It is shown, that the deformation of single crystals occurs practically without increasing of their dimensions in the <110> direction with a total thickness deformation of up to 30%. Direction <110> is characterized by maximum hardening (microhardness) with indentation along it, which causes low plasticity of deformed and annealed foils from Zr-25%Nb alloy at the stretching along and across RD, that is connected with the features of their crystallographic texture.

Surface defect free growth of a spin dimer TlCuCl{sub 3} compound crystals and investigations on its optical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, Gihun, E-mail: G.Ryu@fkf.mpg.de; Son, Kwanghyo

A defect-free high quality single crystal of spin dimer TlCuCl{sub 3} compound is firstly synthesized at the optimal growth temperature using the vertical Bridgman method. In this study, we clearly found that the cupric chloride is easily decomposed into the Cl{sup −} deficient composition at ≥470 °C. The Cl{sup −}- related gas phase at the high temperature region also always gives rise to a pinhole-like surface defect at the surface of crystal. Therefore, we clearly verified an exotic anisotropic magnetic behavior (anisotropic ratio of M{sub b}/M{sub (201)} at 2 K, 7 T=10) using the defect-free TlCuCl{sub 3} crystals in thismore » three-dimensional spin dimer TlCuCl{sub 3} compound, relatively stronger magnetic ordering in the H//b than that of H//(201) direction at above the transition magnetic field. - Graphical abstract: A single crystal of spin dimer TlCuCl{sub 3} compound with a defect free is successfully synthesized on the basis of TG/DTA result. We newly found that this cupric chloride compound is easily decomposed into the Cl{sup −} deficient composition at ≥470 °C and Cl{sup −} related gas phases also give rise to the defects like a pinhole on the surface of TlCuCl{sub 3} crystal. Using the crystals with a surface defect free, we also clearly verified the crystal structure of spin dimer TlCuCl{sub 3} compound.« less

Projection of the Liquidus Surface of the Co - Sn - Bi System

NASA Astrophysics Data System (ADS)

Abilov, Ch. I.; Allazov, M. R.; Sadygova, S. G.

2016-11-01

The crystallization behavior of phases in alloys of the Co - Sn - Bi system is studied by the methods of differential thermal (DTA), x-ray phase (XRP) and x-ray diffraction (XRD) analyses and hardness measurement. The projection of the liquidus surface is plotted. The boundaries of layering, the development of the monovariant processes, and the coordinates of the nonvariant equilibrium compositions are determined. Compositions of (Co3Sn2)1 - x Bi x solid solutions suitable for the production of antifriction materials are suggested.

Crystallization behavior of the Li2S-P2S5 glass electrolyte in the LiNi1/3Mn1/3Co1/3O2 positive electrode layer.

PubMed

Tsukasaki, Hirofumi; Mori, Yota; Otoyama, Misae; Yubuchi, So; Asano, Takamasa; Tanaka, Yoshinori; Ohno, Takahisa; Mori, Shigeo; Hayashi, Akitoshi; Tatsumisago, Masahiro

2018-04-18

Sulfide-based all-solid-state lithium batteries are a next-generation power source composed of the inorganic solid electrolytes which are incombustible and have high ionic conductivity. Positive electrode composites comprising LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) and 75Li 2 S·25P 2 S 5 (LPS) glass electrolytes exhibit excellent charge-discharge cycle performance and are promising candidates for realizing all-solid-state batteries. The thermal stabilities of NMC-LPS composites have been investigated by transmission electron microscopy (TEM), which indicated that an exothermal reaction could be attributed to the crystallization of the LPS glass. To further understand the origin of the exothermic reaction, in this study, the precipitated crystalline phase of LPS glass in the NMC-LPS composite was examined. In situ TEM observations revealed that the β-Li 3 PS 4 precipitated at approximately 200 °C, and then Li 4 P 2 S 6 and Li 2 S precipitated at approximately 400 °C. Because the Li 4 P 2 S 6 and Li 2 S crystalline phases do not precipitate in the single LPS glass, the interfacial contact between LPS and NMC has a significant influence on both the LPS crystallization behavior and the exothermal reaction in the NMC-LPS composites.

High-resolution EPMA X-ray images of mother liquid inclusions in a Pd2Ga single crystal

NASA Astrophysics Data System (ADS)

Müller, D.; Schwerin, J.; Gille, P.; Fehr, K. T.

2014-03-01

During crystal growth from solution inclusions of different compositions were trapped at the rim of a Pd2Ga single crystal. Their fine-grained (< 5 μm) internal structure demands special requirements for electron microprobe analysis, realized by low-voltage (5 keV) element mapping applying a step size of 0.138 μm for each pixel. It can be shown, that these inclusions represent an isolated chemical system, and that crystallisation upon cooling follows the expected thermodynamic phase relations. Thus the final composition in the centre of the inclusion consists of a small-scale mixture of PdGa and Pd5Ga3 evolved out of a solid-solid decomposition of Pd5Ga4.

Oxygen isotope geochemistry of mafic magmas at Mt. Vesuvius

NASA Astrophysics Data System (ADS)

Dallai, Luigi; Raffaello, Cioni; Chiara, Boschi; Claudia, D'oriano

2010-05-01

Pumice and scoria from different eruptive layers of Mt. Vesuvius volcanic products contain mafic minerals consisting of High-Fo olivine and Diopsidic Pyroxene. These phases were crystallized in unerupted trachibasaltic to tephritic magmas, and were brought to surface by large phonolitic/tephri-phonolitic (e.g. Avellino and Pompei) and/or of tephritic and phono-tephritic (Pollena) eruptions. A large set of these mm-sized crystals was accurately separated from selected juvenile material and measured for their chemical compositions (EPMA, Laser Ablation ICP-MS) and 18O/16O ratios (conventional laser fluorination) to constrain the nature and evolution of the primary magmas at Mt. Vesuvius. Uncontaminated mantle δ18O values are hardly recovered in Italian Quaternary magmas, mostly due to the widespread occurrence of crustal contamination of the primary melts during their ascent to the surface (e.g. Alban Hills, Ernici Mts., and Aeolian Islands). At Mt. Vesuvius, measured olivine and clinopyroxene share quite homogeneous chemical compositions (Olivine Fo 85-90 ; Diopside En 45-48, respectively), and represent phases crystallized in near primary mafic magmas. Trace element composition constrains the near primary nature of the phases. Published data on volatile content of melt inclusions hosted in these crystals reveal the coexistence of dissolved water and carbon dioxide, and a minimum trapping pressure around 200-300 MPa, suggesting that crystal growth occurred in a reservoir at about 8-10 km depth. Recently, experimental data have suggested massive carbonate assimilation (up to about 20%) to derive potassic alkali magmas from trachybasaltic melts. Accordingly, the δ18O variability and the trace element content of the studied minerals suggest possible contamination of primary melts by an O-isotope enriched, REE-poor contaminant like the limestone of Vesuvius basement. Low, nearly primitive δ18O values are observed for olivine from Pompeii eruption, although still above the range of typical mantle minerals. The δ18Oolivine and δ18Ocpxof the minerals from all the studied eruptions define variable degrees of carbonate interaction and magma crystallization for the different eruptions, and possibly within the same eruption, and show evidence of oxygen isotope equilibrium at high temperature. However, energy-constrained AFC model suggest that carbonate assimilation was limited. On the basis of our data, we suggest that interaction between magma and a fluxing, decarbonation-derived CO2 fluid may be partly accounted for the measured O-isotope compositions.

Growth of single crystalline delafossite LaCuO2 by the travelling-solvent floating zone method

NASA Astrophysics Data System (ADS)

Mohan, A.; Büchner, B.; Wurmehl, S.; Hess, C.

2014-09-01

Single crystals of LaCuO2 have been grown for the first time using the travelling-solvent floating zone method. The crystal was grown in an Ar-atmosphere by reduction of La2Cu2O5, which was used as the feed rod composition for the growth. The grown crystal has been characterized with regard to phase purity and single crystallinity using powder X-ray diffraction, energy dispersive X-ray analysis, Laue diffraction and scanning electron microscopy.

Exploring high-strength glass-ceramic materials for upcycling of industrial wastes

NASA Astrophysics Data System (ADS)

Back, Gu-Seul; Park, Hyun Seo; Seo, Sung Mo; Jung, Woo-Gwang

2015-11-01

To promote the recycling of industrial waste and to develop value-added products using these resources, the possibility of manufacturing glass-ceramic materials of SiO2-CaO-Al2O3 system has been investigated by various heat treatment processes. Glass-ceramic materials with six different chemical compositions were prepared using steel industry slags and power plant waste by melting, casting and heat treatment. The X-ray diffraction results indicated that diopside and anorthite were the primary phases in the samples. The anorthite phase was formed in SiO2-rich material (at least 43 wt%). In CaO-rich material, the gehlenite phase was formed. By the differential scanning calorimetry analyses, it was found that the glass transition point was in the range of 973-1023 K, and the crystallization temperature was in the range of 1123-1223 K. The crystallization temperature increased as the content of Fe2O3 decreased. By the multi-step heat treatment process, the formation of the anorthite phase was enhanced. Using FactSage, the ratio of various phases was calculated as a function of temperature. The viscosities and the latent heats for the samples with various compositions were also calculated by FactSage. The optimal compositions for glass-ceramics materials were discussed in terms of their compressive strength, and micro-hardness.

Intrinsic Topological Insulator Bi1.5Sb0.5Te3-xSex Thin Crystals

NASA Astrophysics Data System (ADS)

Wang, Wei; Li, Li; Zou, Wenqin; He, Liang; Song, Fengqi; Zhang, Rong; Wu, Xiaoshan; Zhang, Fengming

2015-01-01

The quaternary topological insulator (Bi,Sb)2(Te,Se)3 has demonstrated topological surface states with an insulating bulk. Scientists have identified an optimized composition of Bi1.5Sb0.5Te1.7Se1.3 with the highest resistivity reported. But the physics that drive to this composition remains unclear. Here we report the crystal structure and the magneto-transport properties of Bi1.5Sb0.5Te3-xSex (BSTS) series. A correlation between the structure and the physical properties has been revealed. We found out that within the rhombohedral structure, the composition with most Te substituting Se has the highest resistivity. On the other hand, segregation of other composition phases will introduce much higher bulk concentration.

A 4-D dataset for validation of crystal growth in a complex three-phase material, ice cream

NASA Astrophysics Data System (ADS)

Rockett, P.; Karagadde, S.; Guo, E.; Bent, J.; Hazekamp, J.; Kingsley, M.; Vila-Comamala, J.; Lee, P. D.

2015-06-01

Four dimensional (4D, or 3D plus time) X-ray tomographic imaging of phase changes in materials is quickly becoming an accepted tool for quantifying the development of microstructures to both inform and validate models. However, most of the systems studied have been relatively simple binary compositions with only two phases. In this study we present a quantitative dataset of the phase evolution in a complex three-phase material, ice cream. The microstructure of ice cream is an important parameter in terms of sensorial perception, and therefore quantification and modelling of the evolution of the microstructure with time and temperature is key to understanding its fabrication and storage. The microstructure consists of three phases, air cells, ice crystals, and unfrozen matrix. We perform in situ synchrotron X-ray imaging of ice cream samples using in-line phase contrast tomography, housed within a purpose built cold-stage (-40 to +20oC) with finely controlled variation in specimen temperature. The size and distribution of ice crystals and air cells during programmed temperature cycling are determined using 3D quantification. The microstructural evolution of three-phase materials has many other important applications ranging from biological to structural and functional material, hence this dataset can act as a validation case for numerical investigations on faceted and non-faceted crystal growth in a range of materials.

Size-dependent and tunable crystallization of GeSbTe phase-change nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Bin; Ten Brink, Gert H.; Palasantzas, George; Kooi, Bart J.

2016-12-01

Chalcogenide-based nanostructured phase-change materials (PCMs) are considered promising building blocks for non-volatile memory due to their high write and read speeds, high data-storage density, and low power consumption. Top-down fabrication of PCM nanoparticles (NPs), however, often results in damage and deterioration of their useful properties. Gas-phase condensation based on magnetron sputtering offers an attractive and straightforward solution to continuously down-scale the PCMs into sub-lithographic sizes. Here we unprecedentedly present the size dependence of crystallization for Ge2Sb2Te5 (GST) NPs, whose production is currently highly challenging for chemical synthesis or top-down fabrication. Both amorphous and crystalline NPs have been produced with excellent size and composition control with average diameters varying between 8 and 17 nm. The size-dependent crystallization of these NPs was carefully analyzed through in-situ heating in a transmission electron microscope, where the crystallization temperatures (Tc) decrease when the NPs become smaller. Moreover, methane incorporation has been observed as an effective method to enhance the amorphous phase stability of the NPs. This work therefore elucidates that GST NPs synthesized by gas-phase condensation with tailored properties are promising alternatives in designing phase-change memories constrained by optical lithography limitations.

Studies of Brazilian meteorites. III - Origin and history of the Angra dos Reis achondrite

NASA Technical Reports Server (NTRS)

Prinz, M.; Keil, K.; Hlava, P. F.; Berkley, J. L.; Gomes, C. B.; Curvello, W. S.

1977-01-01

The mineral composition of the Angra dos Reis meteorite, which fell in 1869, is described. This achondrite contains phases reported in a meteorite for the first time. Petrofabric analysis shows that fassaite has a preferred orientation and lineation, which is interpreted as being due to cumulus processes, possibly the effect of post-depositional magmatic current flow or laminar flow of a crystalline mush. The mineral chemistry indicates crystallization from a highly silica-undersaturated melt at low pressure. Several aspects of the mineral composition are discussed with reference to the implications of crystallization conditions.

Effect of heat treatment on phase composition and crystal structure of thin WSi2 films on silicon substrates

NASA Astrophysics Data System (ADS)

Biryukov, Y. P.; Dostanko, A. P.; Maltsev, A. A.; Shakhlevich, G. M.

1984-10-01

An experimental study of WSi2 films on silicon substrates with either 111 or 100 orientation was made, for the purpose of determining the effect of annealing by heat treatment on their phase composition and crystal structure. Films of 0.2 micron thickness were deposited at a rate of 0.5 nm/s on a silicon surface which was predecontaminated of SiO2 layers and adsorbate atoms by ion sputtering in one vacuum cycle. Deposition was by condensation, with the substrate held at various temperatures from 390 to 500 C, and then annealed in an argon atmosphere at various temperatures from 700 to 1000 C for 30 min. Subsequent phase analysis at room temperature was performed with a DRON-2 X-ray diffractometer, using a CuK (sub alpha)-radiation source and covering the 20 = 10 to 130 deg range of angles by the Debye-Sherer method, while the surface morphology was examined under an electron microscope.

Study on crystallization kinetics and phase evolution in Li2O-Al2O3-GeO2-P2O5 glass-ceramics system

NASA Astrophysics Data System (ADS)

Das, Anurup; Dixit, Anupam; Goswami, Madhumita; Mythili, R.; Hajra, R. N.

2018-04-01

To address the safety issues related to liquid electrolyte and improve the battery performance, Solid State Electrolytes (SSEs) are now in frontier area of research interest. We report here synthesis of Li-SSE based on Li2O-Al2O3-GeO2-P2O5 (LAGP) system with NASICON structure. Glass sample with nominal composition Li1.5Al0.5Ge1.5P2.5Si0.5O12 was prepared by melt-quenching technique. Non-isothermal crystallization kinetics was studied using DSC and activation energy of crystallisation was calculated to be ˜ 246 kJ/mol using Kissinger's equation. XRD of heat treated samples show the formation of required LiGe2(PO4)3 phase along with other minor phases. Compositional analysis using SEM-EDX confirms enrichment of Ge and Si along the grain boundaries.

Effect of preparation conditions on the characteristics and photocatalytic activity of TiO2/purified diatomite composite photocatalysts

NASA Astrophysics Data System (ADS)

Sun, Zhiming; Hu, Zhibo; Yan, Yang; Zheng, Shuilin

2014-09-01

TiO2/purified diatomite composite materials were prepared through a modified hydrolysis-deposition method under low temperature using titanium tetrachloride as precursor combined with a calcination crystallization process. The microstructure and crystalline phases of the obtained composites prepared under different preparation conditions were characterized by high resolution scanning electron microscope (SEM) and X-ray diffraction (XRD), respectively. The photocatalytic performance of TiO2/purified diatomite composites was evaluated by Rhodamine B as the target pollutant under UV irradiation, and the optimum preparation conditions of composites were obtained. The TiO2 crystal form in composites prepared under optimum conditions was anatase, the grain size of which was 34.12 nm. The relationships between structure and property of composite materials were analyzed and discussed. It is indicated that the TiO2 nanoparticles uniformly dispersed on the surface of diatoms, and the photocatalytic performance of the composite materials was mainly determined by the dispersity and grain size of loaded TiO2 nanoparticles.

Metal organic chemical vapor deposition of 111-v compounds on silicon

DOEpatents

Vernon, Stanley M.

1986-01-01

Expitaxial composite comprising thin films of a Group III-V compound semiconductor such as gallium arsenide (GaAs) or gallium aluminum arsenide (GaAlAs) on single crystal silicon substrates are disclosed. Also disclosed is a process for manufacturing, by chemical deposition from the vapor phase, epitaxial composites as above described, and to semiconductor devices based on such epitaxial composites. The composites have particular utility for use in making light sensitive solid state solar cells.

Preparation and evaluation of silica-UIO-66 composite as liquid chromatographic stationary phase for fast and efficient separation.

PubMed

Yan, Zhiming; Zheng, Jiangnan; Chen, Jinfeng; Tong, Ping; Lu, Minghua; Lin, Zian; Zhang, Lan

2014-10-31

A silica-UIO-66 composite was fabricated by a simple hydrothermal method and then applied as liquid chromatographic stationary phase for fast and efficient separation. X-ray diffraction patterns showed the presence of UIO-66 crystals in the silica-UIO-66 composites; while scanning electron microscope (SEM) images revealed that silica-UIO-66 composites were a homogeneous mixture of silica bead and UIO-66 crystals. A variety of substituted aromatics, chlorobenzene compounds and polycyclic aromatic hydrocarbons (PAHs) were used to evaluate the retention properties of the silica-UIO-66 composite packed column. Under the optimized conditions, baseline separation of ethylbenzene (EB) and styrene was obtained with high resolution and short retention time. In addition, the silica-UIO-66 composite packed column also showed some advantages in separation of positional isomers, with which baseline separation of EB and xylene, chlorotoluene and dichlorobenzene isomers was achieved. Moreover, the retention mechanisms of these compounds were also discussed in detail. The relative standard deviations (RSDs) for the separation of EB and xylene, chlorotoluene and dichlorobenzene isomers, as well as EB and styrene were 0.42-0.9%, 1.0-1.9%, 0.75-2.0%, and 0.9-2.1% for the retention time, peak area, peak height, and half peak width, respectively. The column efficiencies for EB, p-chlorotoluene, p-dichlorobenzene and styrene were 8780, 9060, 9990 and 5130 plates/m. The successful applications suggested high potentials of silica-MOFs composite as stationary phase for fast and efficient liquid chromatography separation. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermodynamic effects of calcium and iron oxides on crystal phase formation in synthetic gasifier slags containing from 0 to 27wt.% V 2O 3

DOE PAGES

Nakano, Jinichiro; Duchesne, Marc; Bennett, James; ...

2014-11-15

Thermodynamic phase equilibria in synthetic slags (Al 2O 3–CaO–FeO–SiO 2–V 2O 3) were investigated with 0–27 wt.% vanadium oxide corresponding to industrial coal–petroleum coke (petcoke) feedstock blends in a simulated gasifier environment. Samples encompassing coal–petcoke mixed slag compositions were equilibrated at 1500 °C in a 64 vol.% CO/36 vol.% CO 2 atmosphere (Po 2 ≈ 10 –8 atm at 1500 °C) for 72 h, followed by rapid water quench, then analyzed by inductively coupled plasma optical emission spectrometry, X-ray diffractometry, and scanning electron microscopy with wavelength dispersive spectroscopy. With increasing CaO content, FeO content, or both; the slag homogeneity regionmore » expanded and a composition range exhibiting crystals was reduced. The mullite (Al 6Si 2O 13) crystalline phase was not present in the slags above 9 wt.% FeO while the karelianite (V 2O 3) crystalline phase was always present in compositions studied if a sufficient amount of vanadium existed in the slag. Furthermore, based on the present experimental equilibrium evaluation, a set of isothermal phase diagrams showing effects of CaO and FeO on thermodynamic phase stabilities in the vanadium-bearing slags is proposed. Some uses of the diagrams for potential industrial practice are discussed.« less

A Conceptual Model for Shear-Induced Phase Behavior in Crystallizing Cocoa Butter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazzanti,G.; Guthrie, S.; Marangoni, A.

2007-01-01

We propose a conceptual model to explain the quantitative data from synchrotron X-ray diffraction experiments on the shear-induced phase behavior of cocoa butter, the main structural component of chocolate. We captured two-dimensional diffraction patterns from cocoa butter at crystallization temperatures of 17.5, 20.0, and 22.5 {sup o}C under shear rates from 45 to 1440 s{sup -1} and under static conditions. From the simultaneous analysis of the integrated intensity, correlation length, lamellar thickness, and crystalline orientation, we postulate a conceptual model to provide an explanation for the distribution of phases II, IV, V, and X and the kinetics of the process.more » As previously proposed in the literature, we assume that the crystallites grow layer upon layer of slightly different composition. The shear rate and temperature applied define these compositions. Simultaneously, the shear and temperature define the crystalline interface area available for secondary nucleation by promoting segregation and affecting the size distribution of the crystallites. The combination of these factors (composition, area, and size distribution) favors dramatically the early onset of phase V under shear and determines the proportions of phases II, IV, V, and X after the transition. The experimental observations, the methodology used, and the proposed explanation are of fundamental and industrial interest, since the structural properties of crystalline networks are determined by their microstructure and polymorphic crystalline state. Different proportions of the phases will thus result in different characteristics of the final material.« less

The incommensurately modulated(1 - x)Ta 2O 5· xWO 3, 0 ≤ x ≤ 0.267 solid solution

NASA Astrophysics Data System (ADS)

Schmid, Siegbert; Withers, Ray L.; Thompson, John G.

1992-08-01

The phase(1 - x)Ta 2O 5 · WO 3, 0 ≤ x ≤ 0.267 has been studied by X-ray powder diffraction and transmission electron microscopy. It was previously described as an infinite series of anion-deficient, α-UO 3-type "line phases," with compositions resulting from intergrowths of different blocks made up by small numbers of α-UO 3-type cells. More correctly(1 - x)Ta 2O 5· xWO 3, 0 ≤ x ≤ 0.267 is described as an incommensurately modulated structure with a linearly composition-dependent primary modulation wave-vector qprim. = qb*. The underlying orthorhombically distorted α-UO 3-type parent structure has space group symmetry Cmmm ( a ≈ 6.20-6.14, b ≈ 3.66, c ≈ 3.89-3.85Å). Characteristic extinction conditions imply a superspace group symmetry of P : Cmmmm : s, -1,1. The four previously reported crystal structures in the solid solution field are examined by means of apparent valence calculations. Crystal chemical reasons are proposed for the width of the composition range,0 ≤ x ≤ 0.267, observed for the title phase.

Liquid crystalline composites toward organic photovoltaic application (Conference Presentation)

NASA Astrophysics Data System (ADS)

Shimizu, Yo; Sosa-Vargas, Lydia; Shin, Woong; Higuchi, Yumi; Itani, Hiromichi; Kawano, Koki; Dao, Quang Duy; Fujii, Akihiko; Ozaki, Masanori

2017-02-01

Liquid crystalline semiconductor is an interesting category of organic electronic materials and also has been extensively studied in terms of "Printed Electronics". For the wider diversity in research toward new applications, one can consider how to use a combination of miscibility and phase separation in liquid crystals. Here we report discotic liquid crystals in making a composite of which structural order is controlled in nano-scale toward photovoltaic applications. Discotic columnar LCs were studied on their resultant molecular order and carrier transport properties. Liquid crystals of phthalocyanine and its analogues which exhibit columnar mesomorphism with high carrier mobility (10-1 cm2/Vs) were examined with making binary phase diagrams and the correlation to carrier transport properties by TOF measurements was discussed. The shape-analogues in chemical structure shows a good miscibility even for the different lattice-type of columnar arrangement and the carrier mobility is mostly decrease except for a case of combination with a metal-free and the metal complex. For the mixtures with non-mesogenic C60 derivatives, one sees a phase-separated structure due to its immiscibility, though the columnar order is remained in a range of component ratio.Especially, in a range of the ratio, it was observed the phase separated C60 derivatives are fused into the matrix of columnar bundles, indicating C60 derivatives could be diffused in columnar arrays in molecular level.

Conversion of broadband IR radiation and structural disorder in lithium niobate single crystals with low photorefractive effect

NASA Astrophysics Data System (ADS)

Litvinova, Man Nen; Syuy, Alexander V.; Krishtop, Victor V.; Pogodina, Veronika A.; Ponomarchuk, Yulia V.; Sidorov, Nikolay V.; Gabain, Aleksei A.; Palatnikov, Mikhail N.; Litvinov, Vladimir A.

2016-11-01

The conversion of broadband IR radiation when the noncritical phase matching condition is fulfilled in lithium niobate (LiNbO3) single crystals with stoichiometric (R = Li/Nb = 1) and congruent (R = 0.946) compositions, as well as in congruent single crystals doped with zinc has been investigated. It is shown that the spectrum parameters of converted radiation, such as the conversion efficiency, spectral width and position of maximum, depend on the ordering degree of structural units of the cation sublattice along the polar axis of crystal.

Natural and synthetic mineral silicates as functional nanoparticles in polymer composites

NASA Astrophysics Data System (ADS)

Shao, Hua

A new strategy is described for the substantial enhancement of the barrier properties for both a thermoset epoxy polymer and a thermoplastic polyolefin by sandwiching a novel self-supported clay fabric film between thin polymer sheets. The success of this strategy is attributed to the high orientation of clay nanolayers in the paper-like clay fabric films and to the filling of the micro- or sub-micro sized voids between imperfectly tiled clay platelet edges by the polymer chains. Thermoplastic polyolefin-clay fabric film composites were fabricated by hot-pressing the clay films between two sheets of high density polyethylene (HDPE) films. The sandwiched composites exhibit more than a 30-fold decrease in O2 transmission rate with respect to the pure HDPE film. Impregnating the self-supported clay papers with epoxy pre-polymers successfully leads to thermoset composite films with more than 2-3 orders of magnitude reduction in O2 permeability in comparison to the pristine epoxy matrix. Owing to the promising use of synthetic Mg-saponite (denoted SAP) as epoxy polymer reinforcing agents, we investigated the cost-effective synthesis of SAP by replacing urea with sodium hydroxide as base source. Co-crystallization of new zeolite phases, such as garronite (denoted GIS) and cancrinite (denoted CAN), occurred along with SAP upon increasing the alkalinity of the reaction mixture. This finding represents the first example of the preparation of a CAN/SAP phase mixture. Moreover, pure-phase cancrinite with rod-like morphology up to several mum in length was synthesized under Mg-free conditions. Also, the Si/AI ratio within the synthesis gel has an influence on the chemical composition and textural properties of pure CAN crystals. Microporous cancrinite is a promising candidate for reinforcing epoxy polymers, considering that CAN represents a substantial fraction of the mixed CAN-SAP phase formed during the synthesis of saponite. Therefore, the reaction conditions (e.g. alkalinity, reaction temperature, and duration) were further expored in order to optimize the formation of small crystals of CAN (˜ 100 nm) with large external surface area and high pore volume. These textural features facilitate the homogeneous dispersion of cancrinite particles in epoxy matrices. In addition, a new phase sodalite (denoted SOD) was co-crystallized along with CAN in some cases, depending on reaction conditions. The synthetic zeolites CAN and SOD act as reinforcing agents for thermoset epoxy polymers owing in part to their small particle size, large surface area and high pore volume. The tensile strength, modulus and toughness of an epoxy matrix are simultaneously enhanced without the need for organic surface modification of zeolites. This finding represents the first example for which the mechanical properties of glassy epoxy composite are all improved through the use of a microporous zeolite as a functional inorganic nanoparticle.

Controlling the length scale and distribution of the ductile phase in metallic glass composites through friction stir processing

PubMed Central

Arora, Harpreet Singh; Mridha, Sanghita; Grewal, Harpreet Singh; Singh, Harpreet; Hofmann, Douglas C; Mukherjee, Sundeep

2014-01-01

We demonstrate the refinement and uniform distribution of the crystalline dendritic phase by friction stir processing (FSP) of titanium based in situ ductile-phase reinforced metallic glass composite. The average size of the dendrites was reduced by almost a factor of five (from 24 μm to 5 μm) for the highest tool rotational speed of 900 rpm. The large inter-connected dendrites become more fragmented with increased circularity after processing. The changes in thermal characteristics were measured by differential scanning calorimetry. The reduction in crystallization enthalpy after processing suggests partial devitrification due to the high strain plastic deformation. FSP resulted in increased hardness and modulus for both the amorphous matrix and the crystalline phase. This is explained by interaction of shear bands in amorphous matrix with the strain-hardened dendritic phase. Our approach offers a new strategy for microstructural design in metallic glass composites. PMID:27877687

Controlling the length scale and distribution of the ductile phase in metallic glass composites through friction stir processing.

PubMed

Arora, Harpreet Singh; Mridha, Sanghita; Grewal, Harpreet Singh; Singh, Harpreet; Hofmann, Douglas C; Mukherjee, Sundeep

2014-06-01

We demonstrate the refinement and uniform distribution of the crystalline dendritic phase by friction stir processing (FSP) of titanium based in situ ductile-phase reinforced metallic glass composite. The average size of the dendrites was reduced by almost a factor of five (from 24 μ m to 5 μ m) for the highest tool rotational speed of 900 rpm. The large inter-connected dendrites become more fragmented with increased circularity after processing. The changes in thermal characteristics were measured by differential scanning calorimetry. The reduction in crystallization enthalpy after processing suggests partial devitrification due to the high strain plastic deformation. FSP resulted in increased hardness and modulus for both the amorphous matrix and the crystalline phase. This is explained by interaction of shear bands in amorphous matrix with the strain-hardened dendritic phase. Our approach offers a new strategy for microstructural design in metallic glass composites.

Segregation Phenomena on the Crystal Surface of Chemical Compounds

NASA Astrophysics Data System (ADS)

Tomashpol'skii, Yu. Ya.

2018-06-01

The current state of the theoretical and experimental studies of changes in the chemical structure and composition caused by segregation phenomena on the surface of chemical compounds was reviewed. The review considers the experimental data obtained exclusively on single crystals, which were studied by modern instrumental methods, including in situ Auger electron spectrometry, X-ray spectral microanalysis, high-resolution scanning and transmission electron microscopy, secondary electron emission, and atomic force microscopy. The models that suggest the crystal-chemical diffusion and liquid-phase mechanisms of segregation were described. The parameters of the theory include the type of chemical bond, elastic constants, and crystal-chemical characteristics of substances. The models make it possible to predict the nature of changes in the surface composition: segregation tendency, segregant type, and degree of nonstoichiometry. A new direction in surface segregation was considered, which is promising for nanoelectronics and emission electronics.

Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation

NASA Astrophysics Data System (ADS)

Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal

2018-04-01

Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.

Thermal properties of lauric acid filled in carbon nanotubes as shape-stabilized phase change materials.

PubMed

Feng, Yanhui; Wei, Runzhi; Huang, Zhi; Zhang, Xinxin; Wang, Ge

2018-03-14

Carbon nanotubes (CNTs) filled with lauric acid (LA) as a kind of shape-stabilized phase change material were prepared and their structures and phase change properties were characterized. The results showed that the melting point and latent heat of LA confined in carbon nanotubes were lower than those of the bulk material, and both decrease as the diameters of CNTs and the filling ratios of LA decrease. Molecular dynamics (MD) simulations indicated that LA molecules form a liquid layer near pore walls and crystallize at the pore center. When the LA filling ratio was reduced to a certain value, all LA molecules were attached to the inner walls of CNTs, hindering their crystallization. A linear relationship between the melting temperature shift and structural properties was obtained based on the modified Gibbs-Thomson equation, which gives a reliable interpretation of the size effect of nanochannels in phase change materials. We also found that the thermal conductivity of the composite CNTs/LA was four times larger than that of pure LA. This study will provide insights into the design of novel composite phase change materials with better thermal properties by the selection of suitable porous materials and tailoring their pore structures.

Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

USGS Publications Warehouse

Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

2007-01-01

The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent volumetric rate of evolved magma production. ?? Copyright 2007 Oxford University Press.

The solid-solution region for the langasite-type Ca3TaGa3Si2O14 crystal as determined by a lever rule

NASA Astrophysics Data System (ADS)

Zhao, Hengyu; Uda, Satoshi; Maeda, Kensaku; Nozawa, Jun; Koizumi, Haruhiko; Fujiwara, Kozo

2015-04-01

A lever rule was applied to data concerning the compositions and proportions of secondary phases coexisting with a Ca3TaGa3Si2O14 (CTGS) matrix to determine the boundary compositions of the solid-solution region for CTGS at 1320 °C, as a means of ascertaining the solid-solution for the langasite-type phase in the quaternary CaO-Ta2O5-Ga2O3-SiO2 system. The compositions and proportions of secondary phases were assessed by electron probe micro-analysis as well as through back-scattered electron images. The experimental results showed that the narrow solid-solution region for CTGS is located in a Ta-poor, Ga-poor and Si-rich region relative to its stoichiometric composition.

In situ observation of the impact of surface oxidation on the crystallization mechanism of GeTe phase-change thin films by scanning transmission electron microscopy

NASA Astrophysics Data System (ADS)

Berthier, R.; Bernier, N.; Cooper, D.; Sabbione, C.; Hippert, F.; Noé, P.

2017-09-01

The crystallization mechanisms of prototypical GeTe phase-change material thin films have been investigated by in situ scanning transmission electron microscopy annealing experiments. A novel sample preparation method has been developed to improve sample quality and stability during in situ annealing, enabling quantitative analysis and live recording of phase change events. Results show that for an uncapped 100 nm thick GeTe layer, exposure to air after fabrication leads to composition changes which promote heterogeneous nucleation at the oxidized surface. We also demonstrate that protecting the GeTe layer with a 10 nm SiN capping layer prevents nucleation at the surface and allows volume nucleation at a temperature 50 °C higher than the onset of crystallization in the oxidized sample. Our results have important implications regarding the integration of these materials in confined memory cells.

Site specific mineral composition and microstructure of human supra-gingival dental calculus.

PubMed

Hayashizaki, Junko; Ban, Seiji; Nakagaki, Haruo; Okumura, Akihiko; Yoshii, Saori; Robinson, Colin

2008-02-01

Dental calculus has been implicated in the aetiology of several periodontal conditions. Its prevention and removal are therefore desirable clinical goals. While it is known that calculus is very variable in chemical composition, crystallinity and crystallite size little is known about site specific variability within a dentition and between individuals. With this in mind, a study was undertaken to investigate the comparative site specific nature and composition of human dental supra-gingival dental calculus obtained from 66 male patients visiting for their dental check-up using fluorescent X-ray spectroscopy, X-ray diffractometry and Fourier transform infrared spectroscopy. The supra-gingival dental calculus formed on the lingual surfaces of lower anterior teeth and the buccal surfaces of upper molar teeth were classified into four types based on calcium phosphate phases present. There was significant difference in composition of the crystal phase types between lower and upper teeth (p<0.01). There was no significant difference in crystal size between dental calculus on anterior or molar teeth of all samples. The degree of crystallinity of dental calculus formed on the upper molar teeth was higher than that formed on the lower anterior teeth (p<0.01). The CO(3)(2-) contents in dental calculus formed on the lower anterior teeth were higher than on upper molar teeth (p<0.05) which might explain the difference in crystallinity. Magnesium and Si contents and Ca:P ratio on the other hand showed no significant difference between lower and upper teeth. It was concluded that the crystal phases, crystallinity and CO(3)(2-) contents of human dental supra-gingival dental calculus is related to its location in the mouth.

Structural Evolution of Iron Antimonides from Amorphous Precursors to Crystalline Products Studied by Total Scattering Techniques.

PubMed

Bauers, Sage R; Wood, Suzannah R; Jensen, Kirsten M Ø; Blichfeld, Anders B; Iversen, Bo B; Billinge, Simon J L; Johnson, David C

2015-08-05

Homogeneous reaction precursors may be used to form several solid-state compounds inaccessible by traditional synthetic routes, but there has been little development of techniques that allow for a priori prediction of what may crystallize in a given material system. Here, the local structures of FeSbx designed precursors are determined and compared with the structural motifs of their crystalline products. X-ray total scattering and atomic pair distribution function (PDF) analysis are used to show that precursors that first nucleate a metastable FeSb3 compound share similar local structure to the product. Interestingly, precursors that directly crystallize to thermodynamically stable FeSb2 products also contain local structural motifs of the metastable phase, despite their compositional disagreement. While both crystalline phases consist of distorted FeSb6 octahedra with Sb shared between either two or three octahedra as required for stoichiometry, a corner-sharing arrangement indicative of AX3-type structures is the only motif apparent in the PDF of either precursor. Prior speculation was that local composition controlled which compounds nucleate from amorphous intermediates, with different compositions favoring different local arrangements and hence different products. This data suggests that local environments in these amorphous intermediates may not be very sensitive to overall composition. This can provide insight into potential metastable phases which may form in a material system, even with a precursor that does not crystallize to the kinetically stabilized product. Determination of local structure in homogeneous amorphous reaction intermediates from techniques such as PDF can be a valuable asset in the development of systematic methods to prepare targeted solid-state compounds from designed precursors.

Mt. Etna plumbing system revealed by combined textural, compositional, and thermobarometric studies in clinopyroxenes

NASA Astrophysics Data System (ADS)

Giacomoni, P. P.; Coltorti, M.; Bryce, J. G.; Fahnestock, M. F.; Guitreau, M.

2016-04-01

Coupled textural and in situ geochemical studies of clinopyroxene (cpx) phenocrysts, from both historical and recent eruptions of Mt. Etna volcano, provide a means to investigate the processes occurring in the deepest portion of the feeding system (>10 km depth). Five distinct textures were recognized: (1) normal oscillatory zoning, (2) normal zoning with Fe-rich rim, (3) sieve-textured core, (4) reverse oscillatory zoning, and (5) dusty rim. Electron microprobe analyses indicate an almost constant diopside-augite composition, with a slight enrichment in the enstatite for more recent erupted cpx. Core-to-rim compositional profiles, performed along the cpx, reveal distinct compositional characteristics. Normal oscillatory zoning is often characterized by a sharp increase in FeO (Δ ~ 2 wt%) accompanied by a drop in Al2O3 on the outermost 30 μm. Reverse oscillatory zoning, by contrast, exhibits a drop in FeO, Al2O3 (Δ ~ 2 wt%), and a remarkable crystal rim increase in MgO (up to 5 wt%). Similar compositional changes are evident in dusty-textured rims, which are characterized by dissolution edges and overgrowth containing glass pockets and channels. No significant compositional variations have been observed across crystals with sieve-textured cores. Trace element concentrations show enrichments in Sr, La, Zr, and REE, together with a decreasing La/Yb ratio (from ~7 to ~4) in rims of normally zoned crystals. Cpx with reverse zoning and dusty rims has low Sr, La, Zr, and REE contents toward crystal rims. Thermometers and barometers, based on equilibrium cpx-melt pairs, suggest that cpx cores start nucleating at 720 MPa, with the majority of them forming between 600 and 400 MPa but continuing to crystallize until very shallow depths (<100 MPa). Normal oscillatory-zoned phenocrysts surrounded by rims form at pressures shallower than 400 MPa, while reverse zoning and dusty rims occur between 400 and 500 MPa. Coupled petrologic and thermobarometric studies on both clinopyroxenes and plagioclases, associated with detailed textural and in situ geochemical analyses, are promising tools to reconstruct the entire magma ascent path beneath open-system volcanoes. At Mt. Etna, two distinct processes could account for the observed textures: Fe-rich rims in normal oscillatory-zoned crystals can be related to decompression-induced crystallization, while reverse zoning and dusty rims can be produced by mixing with a more basic magma at 400-500 MPa (i.e., ~10 km). Textural features are not restricted to a particular evolutionary phase of the volcano, which suggest that the deep feeding system has not changed significantly since the first alkaline volcanic phase.

Crystal plasticity analysis of stress partitioning mechanisms and their microstructural dependence in advanced steels

DOE PAGES

Pu, Chao; Gao, Yanfei

2015-01-23

Two-phase advanced steels contain an optimized combination of high yield strength and large elongation strain at failure, as a result of stress partitioning between a hard phase (martensite) and a ductile phase (ferrite or austenite). Provided with strong interfaces between the constituent phases, the failure in the brittle martensite phase will be delayed by the surrounding geometric constraints, while the rule of mixture will dictate a large strength of the composite. To this end, the microstructural design of these composites is imperative especially in terms of the stress partitioning mechanisms among the constituent phases. Based on the characteristic microstructures ofmore » dual phase and multilayered steels, two polycrystalline aggregate models are constructed to simulate the microscopic lattice strain evolution of these materials during uniaxial tensile tests. By comparing the lattice strain evolution from crystal plasticity finite element simulations with advanced in situ diffraction measurements in literature, this study investigates the correlations between the material microstructure and the micromechanical interactions on the intergranular and interphase levels. Finally, it is found that although the applied stress will be ultimately accommodated by the hard phase and hard grain families, the sequence of the stress partitioning on grain and phase levels can be altered by microstructural designs. Implications of these findings on delaying localized failure are also discussed.« less

Crystallization of D-mannitol in binary mixtures with NaCl: phase diagram and polymorphism.

PubMed

Telang, Chitra; Suryanarayanan, Raj; Yu, Lian

2003-12-01

To study the crystallization, polymorphism, and phase behavior of D-mannitol in binary mixtures with NaCl to better understand their interactions in frozen aqueous solutions. Differential scanning calorimetry, hot-stage microscopy, Raman microscopy, and variable-temperature X-ray diffractometry were used to characterize D-mannitol-NaCl mixtures. NaCl and D-mannitol exhibited significant melt miscibility (up to 7.5% w/w or 0.20 mole fraction of NaCl) and a eutectic phase diagram (eutectic composition 7.5% w/w NaCl; eutectic temperature 150 degrees C for the alpha and beta polymorphs of D-mannitol and 139 degrees C for the delta). The presence of NaCl did not prevent mannitol from crystallizing but, depending on sample size, affected the polymorph crystallized: below 10 mg, delta was obtained; above 100 mg, alpha was obtained. Pure mannitol crystallized under the same conditions first as the delta polymorph and then as the a polymorph, with the latter nucleating on the former. KCl showed similar eutectic points and melt miscibility with D-mannitol as NaCl. LiCl yielded lower eutectic melting points, inhibited the crystallization of D-mannitol during cooling, and enabled the observation of its glass transition. Despite their structural dissimilarity, significant melt miscibility exists between D-mannitol and NaCl. Their phase diagram has been determined and features polymorph-dependent eutectic points. NaCl influences the polymorphic behavior of mannitol, and the effect is linked to the crystallization of mannitol in two polymorphic stages.

High-throughput screening for thermoelectric sulphides by using crystal structure features as descriptors

NASA Astrophysics Data System (ADS)

Zhang, Ruizhi; Du, Baoli; Chen, Kan; Reece, Mike; Materials Research Insititute Team

With the increasing computational power and reliable databases, high-throughput screening is playing a more and more important role in the search of new thermoelectric materials. Rather than the well established density functional theory (DFT) calculation based methods, we propose an alternative approach to screen for new TE materials: using crystal structural features as 'descriptors'. We show that a non-distorted transition metal sulphide polyhedral network can be a good descriptor for high power factor according to crystal filed theory. By using Cu/S containing compounds as an example, 1600+ Cu/S containing entries in the Inorganic Crystal Structure Database (ICSD) were screened, and of those 84 phases are identified as promising thermoelectric materials. The screening results are validated by both electronic structure calculations and experimental results from the literature. We also fabricated some new compounds to test our screening results. Another advantage of using crystal structure features as descriptors is that we can easily establish structural relationships between the identified phases. Based on this, two material design approaches are discussed: 1) High-pressure synthesis of metastable phase; 2) In-situ 2-phase composites with coherent interface. This work was supported by a Marie Curie International Incoming Fellowship of the European Community Human Potential Program.

Local structural environments of Ge doped in eutectic Sb-Te film before and after crystallization

NASA Astrophysics Data System (ADS)

Shin, Sang Yeol; Cheong, Byung-ki; Choi, Yong Gyu

2018-06-01

Electrical phase change device using the Ge-doped eutectic Sb-Te (e.g., Ge1Sb8Te2) film is known to exhibit improved energy efficiency thanks to lowered threshold voltage as well as decreased power consumption for the reset operation, as compared with Ge2Sb2Te5 film. Ge K-edge EXAFS analysis is employed in this study in an effort to elucidate such merits of Ge1Sb8Te2 film in connection with its local atomic arrangements. It is then verified that a Ge atom is four-fold coordinated in its nearest-neighboring shell both in the as-deposited and in the annealed films. It needs to be highlighted that approximately two Sb atoms constitute the Ge tetrahedral units in its amorphous state; however, after being crystallized, heteropolar Ge-Sb bonds hardly exist in this Ge1Sb8Te2 film. It has been known that crystallization temperature and activation energy for crystallization of this Ge1Sb8Te2 composition are greater than those of Ge2Sb2Te5 composition. In addition, these two phase change materials exhibit distinctly different crystallization mechanisms, i.e., nucleation-dominant for Ge2Sb2Te5 film but growth-dominant for Ge1Sb8Te2 film. These discrepancies in the crystallization-related properties are delineated in terms of the local structural changes verified from the present EXAFS analysis.

Shallow fractionation signature of phase chemistry in Taburiente lavas, La Palma, Canary Islands: Results of MELTS modeling

NASA Astrophysics Data System (ADS)

Guetschow, H. A.; Nelson, B. K.

2002-12-01

Depth of crystal fractionation influences the chemical evolution of ocean island basalts and has significant implications for the physical structures of these volcanoes. In contrast to dominantly shallow systems such as Hawaii, a range of fractionation depths have been reported for Canary Islands lavas. Magmas erupted on La Palma preserve fluid- and melt-inclusion evidence for high-pressure (> 10 kbar) crystallization (Klügel et al., 1998; Hansteen et al., 1998; Nikogosian et al., 2002). If high-pressure fractional crystallization were an early and dominant process, it would generate specific patterns in rock and phase chemistry of eruptive sequences. Alkalic basalts from Taburiente volcano display coherent major element trends consistent with evolution dominated by fractional crystallization while their phenocryst compositions, trace elements, and isotopic trends require mixing between multiple sources. The current model confirms the importance of both fractionation and mixing to achieve the full range of lavas observed. A low-pressure (1 kbar) thermodynamic fractional crystallization model performed with the MELTS (Ghiorso and Sack, 1995) software closely reproduces major element trends from two stratigraphic sequences. This model also predicts the observed sequence of groundmass clinopyroxene compositions and phenocryst zoning reversals. In all low pressure simulations, olivine remains a modally significant liquidus phase during the first 20% and last 30% of the crystallization sequence, resulting in a negative correlation between the CaO and Fo content of olivine. These results are consistent with the presence of olivine phenocrysts that bear petrographic evidence of early crystallization, as well as observed compositional trends of groundmass olivine and clinopyroxene in Taburiente lavas. MELTS models that include an initial period of high pressure (12 kbar) clinopyroxene fractionation produce major element trends comparable to the low pressure model, but also produce high modal volumes of low CaO, high MgO clinopyroxene that are not observed in sections we studied. Removal of such a large quantity of clinopyroxene from the liquid increases the TiO2 and CaO of later-crystallized clinopyroxene to concentrations not observed in our studied sections, and restricts the MgO and FeO* to smaller ranges than observed. Olivine fractionation is restricted to short duration and low abundance late in the crystallization sequence, which is not evident petrographically. The total compositional range of clinopyroxene and olivine crystals observed throughout this suite of rocks is larger than any generated by a single-source MELTS model. Combined with stratigraphically controlled Pb isotope variations it indicates magma mixing and fractionation at low pressures dominates the petrologic diversity in these sections. Hansteen, TH, Klügel, A., Schmincke, H.-U, 1998. Contrib. Min. Pet. 132, 48-64. Klügel, A, 1998. Contrib. Min. Pet. 131, 237-257. Nikogosian, IK, Elliott, T, Touret, JLR. 2002. Chem. Geo. 183, 169-193. Ghiorso, MS, and Sack, RO. Contrib. Min. Pet. 119, 197-212.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salud, J.; Lopez, D.O.; Barrio, M.

The experimental two-component phase diagram between the orientationally disordered crystals 2-amino-2-methyl-1,3-propanediol (AMP) and 1,1,1-tris(hydroxymethyl)propane (PG) has been established from room temperature to the liquid state using thermal analysis and X-ray powder diffraction techniques. The intermolecular interactions in the orientationally disordered mixed crystals of the mentioned system and other related two-component systems are discussed by analyzing the evolution of the packing coefficient as a function of the composition. A thermodynamic analysis of the presented phase diagram and the redetermined AMP/NPG (2,2-dimethyl-1,3-propanediol) is reported on the basis of the enthalpy-entropy compensation theory.

Compositional descriptor-based recommender system for the materials discovery

NASA Astrophysics Data System (ADS)

Seko, Atsuto; Hayashi, Hiroyuki; Tanaka, Isao

2018-06-01

Structures and properties of many inorganic compounds have been collected historically. However, it only covers a very small portion of possible inorganic crystals, which implies the presence of numerous currently unknown compounds. A powerful machine-learning strategy is mandatory to discover new inorganic compounds from all chemical combinations. Herein we propose a descriptor-based recommender-system approach to estimate the relevance of chemical compositions where crystals can be formed [i.e., chemically relevant compositions (CRCs)]. In addition to data-driven compositional similarity used in the literature, the use of compositional descriptors as a prior knowledge is helpful for the discovery of new compounds. We validate our recommender systems in two ways. First, one database is used to construct a model, while another is used for the validation. Second, we estimate the phase stability for compounds at expected CRCs using density functional theory calculations.

Dependences of the density of M{sub 1-x}R{sub x}F{sub 2+x} and R{sub 1-y}M{sub y}F{sub 3-y} single crystals (M = Ca, Sr, Ba, Cd, Pb; R means rare earth elements) on composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sorokin, N. I., E-mail: sorokin@ns.crys.ras.ru; Krivandina, E. A.; Zhmurova, Z. I.

2013-11-15

The density of single crystals of nonstoichiometric phases Ba{sub 1-x}La{sub x}F{sub 2+x} (0 {<=} x {<=} 0.5) and Sr{sub 0.8}La{sub 0.2-x}Lu{sub x}F{sub 2.2} (0 {<=} x {<=} 0.2) with the fluorite (CaF{sub 2}) structure type and R{sub 1-y}Sr{sub y}F{sub 3-y} (R = Pr, Nd; 0 {<=} y {<=} 0.15) with the tysonite (LaF{sub 3}) structure type has been measured. Single crystals were grown from a melt by the Bridgman method. The measured concentration dependences of single crystal density are linear. The interstitial and vacancy models of defect formation in the fluorite and tysonite phases, respectively, are confirmed. To implement themore » composition control of single crystals of superionic conductors M{sub 1-x}R{sub x}F{sub 2+x} and R{sub 1-y}M{sub y}F{sub 3-y} in practice, calibration graphs of X-ray density in the MF{sub 2}-RF{sub 3} systems (M = Ca, Sr, Ba, Cd, Pb; R = La-Lu, Y) are plotted.« less

Interpretation of trace element and isotope features of basalts: relevance of field relations, petrology, major element data, phase equilibria, and magma chamber modeling in basalt petrogenesis

NASA Astrophysics Data System (ADS)

O'Hara, M. J.; Herzberg, C.

2002-06-01

The concentrations and ratios of the major elements determine the physical properties and the phase equilibria behavior of peridotites and basalts in response to the changing energy contents of the systems. The behavior of the trace elements and isotopic features are influenced in their turn by the phase equilibria, by the physical character of the partial melting and partial crystallization processes, and by the way in which a magma interacts with its wall rocks. Concentrating on the trace element and isotope contents of basalts to the exclusion of the field relations, petrology, major element data, and phase equilibria is as improvident as slaughtering the buffalo for the sake of its tongue. The crust is a cool boundary layer and a density filter, which impedes the upward transfer of hot, dense "primary" picritic and komatiitic liquids. Planetary crusts are sites of large-scale contamination and extensive partial crystallization of primitive melts striving to escape to the surface. Escape of truly unmodified primitive melts to the surface is a rare event, requiring the resolution of daunting problems in chemical and mechanical engineering. Primary status for volumetrically abundant basalts such as mid-ocean ridge basalt, ocean island basalt, and continental flood basalts is denied by their low-pressure cotectic character, first remarked upon on petrological grounds in 1928 and on experimental grounds in 1962. These basalt liquids are products of crystal-liquid separation at low pressure. Primary status for these common basalts is further denied by the phase equilibria of such compositions at elevated pressures, when the required residual mantle mineralogy (magnesian olivine and orthopyroxene) is not stable at the liquidus. It is also denied by the picritic or komatiitic nature of partial melts of candidate upper-mantle compositions at high pressures - a conclusion supported by calculation of the melt composition, which would need to be extracted in order to explain the chemical variation between fertile and residual peridotite in natural ultramafic rock suites. The subtleties of magma chamber partial crystallization processes can produce an astounding array of "pseudospidergrams," a small selection of which have been explored here. Major modification of the trace element geochemistry and trace element ratios, even those of the highly incompatible elements, must always be entertained whenever the evidence suggests the possibility of partial crystallization. At one extreme, periodically recharged, periodically tapped magma chambers might undergo partial crystallization by ˜95% consolidation of a succession of small packets of the magma. Refluxing of the 5% residual melts from such a process into the main body of melt would lead to eventual discrimination between highly incompatible elements in that residual liquid comparable with that otherwise achieved by 0.1 to 0.3% liquid extraction in equilibrium partial melting. Great caution needs to be exercised in attempting the reconstruction of more primitive compositions by addition of troctolite, gabbro, and olivine to apparently primitive lava compositions. Special attention is focussed on the phase equilibria involving olivine, plagioclase (i.e., troctolite), and liquid because a high proportion of erupted basalts carry these two phases as phenocrysts, yet the equilibria are restricted to crustal pressures and are only encountered by wide ranges of basaltic compositions at pressures less than 0.5 GPa. The mere presence of plagioclase phenocrysts may be sufficient to disqualify candidate primitive magmas. Determination of the actual contributions of crustal processes to petrogenesis requires a return to detailed field, experimental, and forensic petrologic studies of individual erupted basalt flows; of a multitude of cumulate gabbros and their contacts; and of upper-mantle outcrops.

Synthesis and characterization of bulk metallic glasses prepared by laser direct deposition

NASA Astrophysics Data System (ADS)

Ye, Xiaoyang

Fe-based and Zr-based metallic glasses have attracted extensive interest for structural applications due to their excellent glass forming ability, superior mechanical properties, unique thermal and corrosion properties. In this study, the feasibility of synthesizing metallic glasses with good ductility by laser direct deposition is explored. Both in-situ synthesis with elemental powder mixture and ex-situ synthesis with prealloyed powder are discussed. Microstructure and properties of laser direct deposited metallic glass composites are analyzed. Synthesis of Fe-Cr-Mo-W-Mn-C-Si-B metallic glass composite with a large fraction of amorphous phase was accomplished using laser direct deposition. X-ray diffraction (XRD) and transmission electron microscopy investigations revealed the existence of amorphous structure. Microstructure analyses by optical microscopy and scanning electron microscopy (SEM) indicated the periodically repeated microstructures of amorphous and crystalline phases. Partially crystallized structure brought by laser reheating and remelting during subsequent laser scans aggregated in the overlapping area between each scan. XRD analysis showed that the crystalline particle embedded in the amorphous matrix was Cr 1.07Fe18.93 phase. No significant microstructural differences were found from the first to the last layer. Microhardness of the amorphous phase (HV0.2 1591) showed a much higher value than that of the crystalline phase (HV0.2 947). Macrohardness of the top layer had a value close to the microhardness of the amorphous region. Wear resistance property of deposited layers showed a significant improvement with the increased fraction of amorphous phase. Zr65Al10Ni10Cu15 amorphous composites with a large fraction of amorphous phase were in-situ synthesized by laser direct deposition. X-ray diffraction confirmed the existence of both amorphous and crystalline phases. Laser parameters were optimized in order to increase the fraction of amorphous phase. The microstructure analysis by scanning electron microscopy revealed the deposited structure was composed of periodically repeated amorphous and crystalline phases. Overlapping regions with nanoparticles aggregated were crystallized by laser reheating and remelting processes during subsequent laser scans. Vickers microhardness of the amorphous region showed around 35% higher than that of crystalline region. Average hardness obtained by a Rockwell macrohardness tester was very close to the microhardness of the amorphous region. The compression test showed that the fracture strain of Zr65Al10Ni10Cu15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass. Differential scanning calorimetry test results further revealed the amorphous structure and glass transition temperature Tg was observed to be around 655K. In 3 mol/L NaCl solution, laser direct deposited amorphous composites exhibited distinctly improved corrosion resistance, compared with fully-crystallized samples.

Operation condition for continuous anti-solvent crystallization of CBZ-SAC cocrystal considering deposition risk of undesired crystals

NASA Astrophysics Data System (ADS)

Nishimaru, Momoko; Nakasa, Miku; Kudo, Shoji; Takiyama, Hiroshi

2017-07-01

Crystallization operation of cocrystal production has deposition risk of undesired crystals. Simultaneously, continuous manufacturing processes are focused on. In this study, conditions for continuous cocrystallization considering risk reduction of undesired crystals deposition were investigated on the view point of thermodynamics and kinetics. The anti-solvent cocrystallization was carried out in four-component system of carbamazepine, saccharin, methanol and water. From the preliminary batch experiment, the relationships among undesired crystal deposition, solution composition decided by mixing ratio of solutions, and residence time for the crystals were considered, and then the conditions of continuous experiment were decided. Under these conditions, the continuous experiment was carried out. The XRD patterns of obtained crystals in the continuous experiment showed that desired cocrystals were obtained without undesired crystals. This experimental result was evaluated by using multi-component phase diagrams from the view point of the operation point's movement. From the evaluation, it was found that there is a certain operation condition which the operation point is fixed with time in the specific domain without the deposition risk of undesired single component crystals. It means the possibility of continuous production of cocrystals without deposition risk of undesired crystals was confirmed by using multi-component phase diagrams.

Influence of non-covalent modification of multiwalled carbon nanotubes on the crystallization behaviour of binary blends of polypropylene and polyamide 6.

PubMed

Mukhopadhyay, Nabaneeta; Panwar, Ajay S; Kumar, Gulshan; Samajdar, I; Bhattacharyya, Arup R

2015-02-14

Blends of polypropylene (PP) and polyamide 6 (PA6) with multiwalled carbon nanotubes (MWNTs) were prepared using different processing strategies in a twin-screw micro-compounder. The effect of MWNTs on the crystallization behaviour of the PP phase and the PA6 phase of the blend has been investigated through non-isothermal crystallization studies by differential scanning calorimetric analysis. Furthermore, the effect of the addition of the compatibilizer (PP-g-MA) and the modification of MWNTs (m-MWNTs) with a non-covalent organic modifier (Li-salt of 6 amino hexanoic acid, Li-AHA) has also been studied in context to the crystallization behaviour of the PP and PA6 phase in the blend. The crystallization studies have indicated a significant increase in bulk crystallization temperature of the PP phase in the blend in the presence of MWNTs. Moreover, the formation of 'trans-lamellar crystalline' structure consisting of PA6 'trans-crystalline lamellae' on MWNTs surface was facilitated in the case of blends prepared via 'protocol 2' as compared to the corresponding blends prepared via 'protocol 1'. Wide angle X-ray diffraction analysis has showed the existence of a β-polymorph of the PP phase due to incorporation of the PA6 phase in the blend. Addition of MWNTs in the blends has facilitated further β-crystalline structure formation of the PP phase. In the presence of m-MWNTs, a higher β-fraction was observed in the PP phase as compared to the blend with pristine MWNTs. Addition of PP-g-MA has suppressed the β-phase formation in the PP phase in the blend. X-ray bulk texture analysis revealed that incorporation of PA6 as well as pristine/modified MWNTs has influenced the extent of orientation of the PP chains towards specific crystalline planes in various blend compositions of PP and PA6.

Chemical composition, crystal size and lattice structural changes after incorporation of strontium into biomimetic apatite.

PubMed

Li, Z Y; Lam, W M; Yang, C; Xu, B; Ni, G X; Abbah, S A; Cheung, K M C; Luk, K D K; Lu, W W

2007-03-01

Recently, strontium (Sr) as ranelate compound has become increasingly popular in the treatment of osteoporosis. However, the lattice structure of bone crystal after Sr incorporation is yet to be extensively reported. In this study, we synthesized strontium-substituted hydroxyapatite (Sr-HA) with different Sr content (0.3%, 1.5% and 15% Sr-HA in mole ratio) to simulate bone crystals incorporated with Sr. The changes in chemical composition and lattice structure of apetite after synthetic incorporation of Sr were evaluated to gain insight into bone crystal changes after incorporation of Sr. X-ray diffraction (XRD) patterns revealed that 0.3% and 1.5% Sr-HA exhibited single phase spectrum, which was similar to that of HA. However, 15% Sr-HA induced the incorporation of HPO4(2-) and more CO3(2-), the crystallinity reduced dramatically. Transmission electron microscopy (TEM) images showed that the crystal length and width of 0.3% and 1.5% Sr-HA increased slightly. Meanwhile, the length and width distribution were broadened and the aspect ratio decreased from 10.68+/-4.00 to 7.28+/-2.80. The crystal size and crystallinity of 15% Sr-HA dropped rapidly, which may suggest that the fundamental crystal structure is changed. The findings from this work indicate that current clinical dosage which usually results in Sr incorporation of below 1.5% may not change chemical composition and lattice structure of bone, while it will broaden the bone crystal size distribution and strengthen the bone.

Impact of spherical nanoparticles on nematic order parameters

NASA Astrophysics Data System (ADS)

Kyrou, C.; Kralj, S.; Panagopoulou, M.; Raptis, Y.; Nounesis, G.; Lelidis, I.

2018-04-01

We study experimentally the impact of spherical nanoparticles on the orientational order parameters of a host nematic liquid crystal. We use spherical core-shell quantum dots that are surface functionalized to promote homeotropic anchoring on their interface with the liquid crystal host. We show experimentally that the orientational order may be strongly affected by the presence of spherical nanoparticles even at low concentrations. The orientational order of the composite system is probed by means of polarized micro-Raman spectroscopy and by optical birefringence measurements as function of temperature and concentration. Our data show that the orientational order depends on the concentration in a nonlinear way, and the existence of a crossover concentration χc≈0.004 pw . It separates two different regimes exhibiting pure-liquid crystal like (χ <χc ) and distorted-nematic ordering (χ >χc ), respectively. In the latter phase the degree of ordering is lower with respect to the pure-liquid crystal nematic phase.

Structural transformation in antiferroelectric PbZrO3-relaxor ferroelectric Pb(Ni1/3Nb2/3)O3 solid solution system

NASA Astrophysics Data System (ADS)

Wirunchit, S.; Vittayakorn, N.

2008-07-01

The solid solution between the antiferroelectric (AFE) PbZrO3 (PZ) and the relaxor ferroelectric (FE) Pb(Ni1/3Nb2/3)O3 (PNN) was synthesized by the columbite precursor method. The crystal structure, phase transformations, and dielectric and thermal properties of (1-x )PZ-xPNN where x =0.00-0.30 were investigated. With these data, the FE phase diagram between PZ and PNN has been established. The crystal structure data obtained from X-ray diffraction indicate that the solid solution PZ-PNN, where x =0.00-0.30, successively transforms from orthorhombic to rhombohedral symmetry with an increase in the PNN concentration. The AFE phase→FE phase transition occurs in compositions of 0.00⩽x⩽0.08. The AFE →FE phase transition shifts to lower temperatures with higher compositions of x. The FE phase temperature range width increases with increased PNN. Apparently the replacement of the Zr4+ ion by Ni2+/Nb5+ ions decreases the driving force for an antiparallel shift of Pb2+ ions because they interrupt the translational symmetry and facilitates the appearance of a rhombohedral FE phase when the amount of PNN is higher than 8mol%.

Growth and characterization of CaFe1-xCoxAsF single crystals by CaAs flux method

NASA Astrophysics Data System (ADS)

Ma, Yonghui; Hu, Kangkang; Ji, Qiucheng; Gao, Bo; Zhang, Hui; Mu, Gang; Huang, Fuqiang; Xie, Xiaoming

2016-10-01

Millimeter sized single crystals of CaFe1-x Cox AsF were grown using a self-flux method. It is found that high-quality single crystals can be grown from three approaches with different initial raw materials. The chemical compositions and crystal structure were characterized carefully. Compared with the undoped parent phase CaFeAsF, the crystal lattice along the c-axis is suppressed by the Co substitution while that along the a-axis expands slightly. Superconductivity with the critical transition Tc as high as 21 K was confirmed by both the resistivity and magnetic susceptibility measurements in the sample with x=0.118. Moreover, it is found that Tc can be enhanced for about 1 K under the very small hydrostatic pressure of 0.22 GPa, which is more quick than that reported in the polycrystalline samples. Our results are a promotion for the physical investigations of 1111 phase iron-pnictide superconductors.

Raman and IR Spectroscopic Study of Hydrous Pyroxenes

NASA Astrophysics Data System (ADS)

Kung, J.; Li, C.; Stalder, R.; Inoue, T.; Chuang, S.; Balfan-Casanova, N.; Skogby, H.

2017-12-01

Pyroxene group is one of major composed minerals at upper mantle and is nominally anhydrous mineral (NAM), in terms of its crystal chemistry. The analysis of field specimens showed the mantle-derived pyroxene phase containing some amount of hydrogen within crystal structure, the major incorporation mechanism to be as hydroxyl, OH¯, which chemical component treats as `water', H2O. Compared with the other mantle-derived olivine and garnet, the crystal chemistry of pyroxene phases (opx and cpx) is more complex that can result in different OH¯ bonding environments that would greatly affect the geophysics-interested physical properties, for example, elasticity and transport properties. In order to understand how the hydroxyl bonding condition with different composition of opx and cpx in this study, IR and Raman spectroscopies were employed to investigate the lattice modes and hydroxyl-bonding environments with different composition and crystal structures. The studied pyroxene specimens included natural hydrous pyroxenes and synthesized hydrous orthoenstatite (OEN) at high pressure and temperature (4-7 GPa, 1300-1400°C). The measured IR band range was carried out from 2800 to 3600 cm-1 and the Raman range from 50 to 3600 cm-1. The analysis showed that the band of 3600 cm-1 is the major feature in natural opx specimens but its intensity would be varied in different crystal orientation. For synthesized OEN, the number of observed IR band is higher than that reported in previous studies. The common major bands observed in natural cpx are around 3500 cm-1. The Raman measurement of studied specimen is to characterize the variation of Raman mode as function of composition and possible Raman active hydroxyl-related modes. In this meeting the results will be presented and discussed.

Synthesis of nano anatase for titanosilicate ETS-10 synthesis

NASA Astrophysics Data System (ADS)

Shafeque, Shihara

Functionalized textiles present a vast and growing niche in the global textile market at US $400 billion [1, 2]. Engelhard Titanium Silicate 10 (ETS-10), a photocatalytic zeo-type material if coated on textiles, is expected to impart useful properties similar to TiO2, such as stain-resistant, odor repellant, bactericidal and enhanced UV protection [3, 4]. Typically, small ETS-10 crystals of size ˜300-800 nm are synthesized using solid titania (e.g., anatase or P25) sources [5, 6, 7]. However, smaller ETS-10 crystals are required for a uniform surface coating with highly effective surface area. The dissolution of titania particles (i.e., their size) is hypothesized to be important in small ETS-10 crystal formation [5, 6, 7]. Nano anatase was synthesized by modification of two methods: direct precipitation [7] and sol-gel synthesis [3]. Analysis by XRD confirmed that both methods produced nano anatase of crystallite size ˜4-5 nm. However, FE-SEM analysis showed that product from direct precipitation, existed as intergrown spheroidal particles with size ˜1.0 mum. These particles dispersed poorly in deionized water. Therefore, the best nano anatase samples were from sol-gel synthesis in two forms, dry powder and colloidal anatase. ETS-10 synthesis was investigated using two methods adopted from literature [6, 7]. The method of Yoon and co-workers [7], with nano anatase in a molar composition of 5.5TEOS: TiO2: 8.4NaOH: 1.43KF: 350H2O: 2.2H2SO4 produced unknown phase(s) with some ETS-10 and quartz. Using colloidal anatase with molar composition 5.5TEOS:1.0TiO 2:8.4NaOH:1.43KF:400H2O:2.2H2SO4 also produced unknown phase(s). The method of Anderson and co-workers [6] with nano anatase powder in a molar composition of 5.5SiO2: TiO 2: 5.2Na2O: 0.5K2O: 113H2O produced quartz with ETS-10 impurity. When colloidal anatase was used, with molar composition TiO2:5.5SiO2:5.2Na2O:0.5K2O:332H 2O, unreacted anatase and quartz were formed. It was hypothesized that the very low reaction mixture pH of ˜4.1 was responsible for the absence of ETS-10. Therefore, pH of this mixture was modified between ˜6.55-12.75.At low pH of ˜6.55 unreacted anatase was present, while, pH higher than ˜11.24 formed ETS-4 crystals. At an "optimum" pH of ˜11.24 nearly phase-pure ETS-10 crystals were formed. However, these ETS-10 crystals were not small but ˜10-20 mum. This is the first time, that colloidal anatase has been utilized for ETS-10 synthesis.

Crystal phase identification

DOEpatents

Michael, Joseph R.; Goehner, Raymond P.; Schlienger, Max E.

2001-01-01

A method and apparatus for determining the crystalline phase and crystalline characteristics of a sample. This invention provides a method and apparatus for unambiguously identifying and determining the crystalline phase and crystalline characteristics of a sample by using an electron beam generator, such as a scanning electron microscope, to obtain a backscattered electron Kikuchi pattern of a sample, and extracting crystallographic and composition data that is matched to database information to provide a quick and automatic method to identify crystalline phases.

Structure of initial crystals formed during human amelogenesis

NASA Astrophysics Data System (ADS)

Cuisinier, F. J. G.; Voegel, J. C.; Yacaman, J.; Frank, R. M.

1992-02-01

X-ray diffraction analysis revealed only the existence of carbonated hydroxyapatite (c.HA) during amelogenesis, whereas conventional transmission electron microscopy investigations showed that developing enamel crystals have a ribbon-like habit. The described compositional changes could be an indication for the presence of minerals different from c.HA. However, the absence of identification of such a mineral shows the need of studies by high resolution electron microscopy (HREM) of initial formed human enamel crystals. We demonstrate the existence of two crystal families involved in the early stages of biomineralization: (a) nanometer-size particles which appeared as a precursor phase; (b) ribbon-like crystals, with a structure closely related to c.HA, which by a progressive thickening process tend to attain the mature enamel crystal habit.

Glass precursor approach to high-temperature superconductors

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1992-01-01

The available studies on the synthesis of high T sub c superconductors (HTS) via the glass precursor approach were reviewed. Melts of the Bi-Sr-Ca-Cu-O system as well as those doped with oxides of some other elements (Pb, Al, V, Te, Nb, etc.) could be quenched into glasses which, on further heat treatments under appropriate conditions, crystallized into the superconducting phase(s). The nature of the HTS phase(s) formed depends on the annealing temperature, time, atmosphere, and the cooling rate and also on the glass composition. Long term annealing was needed to obtain a large fraction of the 110 K phase. The high T sub c phase did not crystallize out directly from the glass matrix, but was preceded by the precipitation of other phases. The 110 K HTS was produced at high temperatures by reaction between the phases formed at lower temperatures resulting in multiphase material. The presence of a glass former such as B2O3 was necessary for the Y-Ba-Cu-O melt to form a glass on fast cooling. A discontinuous YBa2Cu3O(7-delta) HTS phase crystallized out on heat treatment of this glass. Attempts to prepare Tl-Ba-Ca-Cu-O system in the glassy state were not successful.

Visual observation of gas hydrates nucleation and growth at a water - organic liquid interface

NASA Astrophysics Data System (ADS)

Stoporev, Andrey S.; Semenov, Anton P.; Medvedev, Vladimir I.; Sizikov, Artem A.; Gushchin, Pavel A.; Vinokurov, Vladimir A.; Manakov, Andrey Yu.

2018-03-01

Visual observation of nucleation sites of methane and methane-ethane-propane hydrates and their further growth in water - organic liquid - gas systems with/without surfactants was carried out. Sapphire Rocking Cell RCS6 with transparent sapphire cells was used. The experiments were conducted at the supercooling ΔTsub = 20.2 °C. Decane, toluene and crude oils were used as organics. Gas hydrate nucleation occurred on water - metal - gas and water - sapphire - organic liquid three-phase contact lines. At the initial stage of growth hydrate crystals rapidly covered the water - gas or water - organics interfaces (depending on the nucleation site). Further hydrate phase accrete on cell walls (sapphire surface) and into the organics volume. At this stage, growth was accompanied by water «drawing out» from under initial hydrate film formed at water - organic interface. Apparently, it takes place due to water capillary inflow in the reaction zone. It was shown that the hydrate crystal morphology depends on the organic phase composition. In the case of water-in-decane emulsion relay hydrate crystallization was observed in the whole sample, originating most likely due to the hydrate crystal intergrowth through decane. Contacts of such crystals with adjacent water droplets result in rapid hydrate crystallization on this droplet.

Improved photovoltaic performance from inorganic perovskite oxide thin films with mixed crystal phases

NASA Astrophysics Data System (ADS)

Chakrabartty, Joyprokash; Harnagea, Catalin; Celikin, Mert; Rosei, Federico; Nechache, Riad

2018-05-01

Inorganic ferroelectric perovskites are attracting attention for the realization of highly stable photovoltaic cells with large open-circuit voltages. However, the power conversion efficiencies of devices have been limited so far. Here, we report a power conversion efficiency of 4.20% under 1 sun illumination from Bi-Mn-O composite thin films with mixed BiMnO3 and BiMn2O5 crystal phases. We show that the photocurrent density and photovoltage mainly develop across grain boundaries and interfaces rather than within the grains. We also experimentally demonstrate that the open-circuit voltage and short-circuit photocurrent measured in the films are tunable by varying the electrical resistance of the device, which in turn is controlled by externally applying voltage pulses. The exploitation of multifunctional properties of composite oxides provides an alternative route towards achieving highly stable, high-efficiency photovoltaic solar energy conversion.

Preparation and electrocatalytic activity of tungsten carbide and titania nanocomposite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Sujuan; Shi, Binbin; Yao, Guoxing

2011-10-15

Graphical abstract: The electrocatalytic activity of tungsten carbide and titania nanocomposite is related to the structure, crystal phase and chemical components of the nanocomposite, and is also affected by the property of electrolyte. A synergistic effect exists between tungsten carbide and titania of the composite. Highlights: {yields} Electrocatalytic activity of tungsten carbide and titania nanocomposite with core-shell structure. {yields} Activity is related to the structure, crystal phase and chemical component of the nanocomposite. {yields} The property of electrolyte affects the electrocatalytic activity. {yields} A synergistic effect exists between tungsten carbide and titania of the composite. -- Abstract: Tungsten carbide andmore » titania nanocomposite was prepared by combining a reduced-carbonized approach with a mechanochemical approach. The samples were characterized by X-ray diffraction, transmission electron microscope under scanning mode and X-ray energy dispersion spectrum. The results show that the crystal phases of the samples are composed of anatase, rutile, nonstoichiometry titanium oxide, monotungsten carbide, bitungsten carbide and nonstoichiometry tungsten carbide, and they can be controlled by adjusting the parameters of the reduced-carbonized approach; tungsten carbide particles decorate on the surface of titania support, the diameter of tungsten carbide particle is smaller than 20 nm and that of titania is around 100 nm; the chemical components of the samples are Ti, O, W and C. The electrocatalytic activity of the samples was measured by a cyclic voltammetry with three electrodes. The results indicate that the electrocatalytic activities of the samples are related to their crystal phases and the property of electrolyte in aqueous solution. A synergistic effect between titania and tungsten carbide is reported for the first time.« less

Phase stability, crystal structure and magnetism in (U1-xNbx)2 Ni21B6 and (UyNb1-y)3Ni20B6

NASA Astrophysics Data System (ADS)

Provino, Alessia; Bhattacharya, Amitava; Dhar, Sudesh K.; Pani, Marcella; Gatti, Flavio; Paudyal, Durga; Manfrinetti, Pietro

Ternary phases with composition T2M21X6 and T3M20X6 (T = transition metal; M = 3 d metal; X = B, C, P) are reported to crystallize with the W2Cr21C6-type and Mg3Ni20B6-type, respectively (ternary ordered derivatives of the cubic Cr23C6-type, cF116). They attract interest due to their refractory, mechanical, and peculiar magnetic properties. Literature data on these compounds only concern apparently stoichiometric 2:21:6 and 3:20:6 phases. Often only nominal composition has been reported, with few structural refinements and no measurements of physical properties. Lack of detailed stoichiometry and crystallographic data does not allow sufficient understanding of the crystal chemistry and properties of these compounds. We studied stability, crystal structure and magnetism of (U1-xNbx)2 Ni21B6 and (UyNb1-y)3Ni20B6; stable phases are U2Ni21B6 and Nb3Ni20B6, as also confirmed by theoretical calculations. The two pristine compounds solubilize Nb and U, respectively, up to a given extent. The substitution of U by Nb leads to a structural change from the W2Cr21C6- to the Mg3Ni20B6-type. While U2Ni21B6 is a Pauli paramagnet (itinerant non-magnetic state of U-5 f electrons), in agreement with literature, magnetization data for (UyNb1-y)3 Ni20B6 show itinerant ferromagnetism with TC >300 K.

Thermal Regulation of Heat Transfer Processes

DTIC Science & Technology

2014-10-02

determine the contrasts of thermophysical properties of composites and thin films , and various approaches to regulate heat transport processes. In the...nanofluids, 2) thermal regulation of optical properties in thin film , and 3) thermal regulation of phase transition for efficient steam generation...stress generated during the crystals growth forces CNTs to contact with each other and form a conductive percolation network. Hence the composite

Crystal structure, Raman scattering and magnetic properties of CuCr2-xZrxSe4 and CuCr2-xSnxSe4 selenospinels

NASA Astrophysics Data System (ADS)

Pinto, C.; Galdámez, A.; Barahona, P.; Moris, S.; Peña, O.

2018-06-01

Selenospinels, CuCr2-xMxSe4 (M = Zr and Sn), were synthesized via conventional solid-state reactions. The crystal structure of CuCr1.5Sn0.5Se4, CuCr1.7Sn0.3Se4, CuCr1.5Zr0.5Se4, and CuCr1.8Zr0.2Se4 were determined using single-crystal X-ray diffraction. All the phases crystallized in a cubic spinel-type structure. The chemical compositions of the single-crystals were examined using energy-dispersive X-ray analysis (EDS). Powder X-ray diffraction patterns of CuCr1.3Sn0.7Se4 and CuCr1.7Sn0.3Se4 were consistent with phases belonging to the Fd 3 bar m Space group. An analysis of the vibrational properties on the single-crystals was performed using Raman scattering measurements. The magnetic properties showed a spin glass behavior with increasing Sn content and ferromagnetic order for CuCr1.7Sn0.3Se4.

High Performance Relaxor-Based Ferroelectric Single Crystals for Ultrasonic Transducer Applications

PubMed Central

Chen, Yan; Lam, Kwok-Ho; Zhou, Dan; Yue, Qingwen; Yu, Yanxiong; Wu, Jinchuan; Qiu, Weibao; Sun, Lei; Zhang, Chao; Luo, Haosu; Chan, Helen L. W.; Dai, Jiyan

2014-01-01

Relaxor-based ferroelectric single crystals Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) have drawn much attention in the ferroelectric field because of their excellent piezoelectric properties and high electromechanical coupling coefficients (d33∼2000 pC/N, kt∼60%) near the morphotropic phase boundary (MPB). Ternary Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) single crystals also possess outstanding performance comparable with PMN-PT single crystals, but have higher phase transition temperatures (rhombohedral to tetragonal Trt, and tetragonal to cubic Tc) and larger coercive field Ec. Therefore, these relaxor-based single crystals have been extensively employed for ultrasonic transducer applications. In this paper, an overview of our work and perspectives on using PMN-PT and PIN-PMN-PT single crystals for ultrasonic transducer applications is presented. Various types of single-element ultrasonic transducers, including endoscopic transducers, intravascular transducers, high-frequency and high-temperature transducers fabricated using the PMN-PT and PIN-PMN-PT crystals and their 2-2 and 1-3 composites are reported. Besides, the fabrication and characterization of the array transducers, such as phased array, cylindrical shaped linear array, high-temperature linear array, radial endoscopic array, and annular array, are also addressed. PMID:25076222

Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis.

PubMed

Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

2015-06-04

Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, Co(x)Mn(3-x)O4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

Structure and temperature-dependent phase transitions of lead-free Bi 1/2Na 1/2TiO 3-Bi 1/2K 1/2TiO 3-K 0.5Na 0.5NbO 3 piezoceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anton, Eva-Maria; Schmitt, Ljubomira Ana; Hinterstein, Manuel

2014-05-28

Structure and phase transitions of (1-y)((1-x)Bi 1/2Na 1/2TiO 3-xBi 1/2K 1/2TiO 3)-yK 0.5Na 0.5NbO 3 (x; y) piezoceramics (0.1 ≤ x ≤ 0.4; 0 ≤ y ≤ 0.05) were investigated by transmission electron microscopy, neutron diffraction, temperature-dependent x-ray diffraction, and Raman spectroscopy. The local crystallographic structure at room temperature (RT) does not change by adding K 0.5Na 0.5NbO 3 to Bi 1/2Na 1/2TiO 3-xBi 1/2K 1/2TiO 3 for x = 0.2 and 0.4. The average crystal structure and microstructure on the other hand develop from mainly long-range polar order with ferroelectric domains to short-range order with polar nanoregions displaying amore » more pronounced relaxor character. The (0.1; 0) and (0.1; 0.02) compositions exhibit monoclinic Cc space group symmetry, which transform into Cc + P4bm at 185 and 130 °C, respectively. This high temperature phase is stable at RT for the morphotropic phase boundary compositions of (0.1; 0.05) and all compositions with x = 0.2. For the compositions of (0.1; 0) and (0.1; 0.02), local structural changes on heating are evidenced by Raman; for all other compositions, changes in the long-range average crystal structure were observed.« less

Faceting, composition and crystal phase evolution in III-V antimonide nanowire heterostructures revealed by combining microscopy techniques.

PubMed

Xu, Tao; Dick, Kimberly A; Plissard, Sébastien; Nguyen, Thanh Hai; Makoudi, Younes; Berthe, Maxime; Nys, Jean-Philippe; Wallart, Xavier; Grandidier, Bruno; Caroff, Philippe

2012-03-09

III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.

Advanced methods for preparation and characterization of infrared detector materials. [mercury cadmium tellurides

NASA Technical Reports Server (NTRS)

Lehoczky, S. L.; Szofran, F. R.; Martin, B. G.

1980-01-01

Mercury cadmium telluride crystals were prepared by the Bridgman method with a wide range of crystal growth rates and temperature gradients adequate to prevent constitutional supercooling under diffusion-limited, steady state, growth conditions. The longitudinal compositional gradients for different growth conditions and alloy compositions were calculated and compared with experimental data to develop a quantitative model of the crystal growth kinetics for the Hg(i-x)CdxTe alloys, and measurements were performed to ascertain the effect of growth conditions on radial compositional gradients. The pseudobinary HgTe-CdTe constitutional phase diagram was determined by precision differential thermal analysis measurements and used to calculate the segregation coefficient of Cd as a function of x and interface temperature. Computer algorithms specific to Hg(1-x)CdxTe were developed for calculations of the charge carrier concentrations, charge carrier mobilities, Hall coefficient, optical absorptance, and Fermi energy as functions of x, temperature, ionized donor and acceptor concentrations, and neutral defect concentrations.

Defect Structures of La1 - y Sr y F3 - y , La1 - y Ba y F3 - y , and Nd1 - y Ca y F3 - y ( y = 0.05, 0.10) Nonstoichiometric Tysonite Phases

NASA Astrophysics Data System (ADS)

Chernaya, T. S.; Verin, I. A.; Khrykina, O. N.; Bolotina, N. B.

2018-01-01

Characteristic features of defect structures of La1 - y Sr y F3 - y , La1 - y Ba y F3 - y , and Nd1 - y Ca y F3 - y ( y = 0.05, 0.10) nonstoichiometric phases of different compositions are determined from X-ray diffraction data. Interest in subtle details of their structure is determined by the possibility of ion transport over fluorine vacancies and by a strong compositional dependence of the ionic conductivity. The La0.95Sr0.05F2.95, La0.95Ba0.05F2.95, and Nd0.95Ca0.05F2.95 phases, as well as the La0.9Ba0.1F2.9 phase, crystallize as β-LaF3 (sp. gr. P3̅c1, Z = 6). The La0.9Sr0.1F2.9 and Nd0.9Ca0.1F2.9 phases lose their superstructure and are described by a cell whose volume is three times smaller (sp. gr. P63/ mmc, Z = 2). Defects of crystal structure R1 - y M y F3 - y are not exhausted by vacancies in fluorine positions. All crystals with a "large" cell are twinned according to the merohedral twin law. The majority of atomic positions in models with a "small" cell are split by group symmetry elements and are occupied statistically.

Mott localization in a pure stripe antiferromagnet Rb 1 - δ Fe 1.5 - σ S 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Yi, Ming; Cao, Huibo

A combination of neutron diffraction and angle-resolved photoemission spectroscopy measurements on a pure antiferromagnetic stripe Rb 1-δFe 1.5-σS 2 is reported. A neutron diffraction experiment on a powder sample shows that a 98% volume fraction of the sample is in the antiferromagnetic stripe phase with rhombic iron vacancy order and a refined composition of Rb 0.66Fe 1.36S 2, and that only 2% of the sample is in the block antiferromagnetic phase with √5×√5 iron vacancy order. Furthermore, a neutron diffraction experiment on a single crystal shows that there is only a single phase with the stripe antiferromagnetic order with themore » refined composition of Rb 0.78Fe 1.35S 2, while the phase with block antiferromagnetic order is absent. Angle-resolved photoemission spectroscopy measurements on the same crystal with the pure stripe phase reveal that the electronic structure is gapped at the Fermi level with a gap larger than 0.325 eV. The data collectively demonstrate that the extra 10% iron vacancies in addition to the rhombic iron vacancy order effectively impede the formation of the block antiferromagnetic phase; the data also suggest that the stripe antiferromagnetic phase with rhombic iron vacancy order is a Mott insulator.« less

Stimulation of processes of self-propagating high temperature synthesis in system Ti + Al at low temperatures by influence of γ-quanta

NASA Astrophysics Data System (ADS)

Sobachkin, A. V.; Loginova, M. V.; Sitnikov, A. A.; Yakovlev, V. I.; Filimonov, V. Yu; Gradoboev, A. V.

2018-03-01

In the present work, the influence of the irradiation with gamma-quanta 60Co upon the structural and phase state of the components of the mechanically activated powder composition of Ti+Al is investigated. The phase composition, structural parameters, and crystallinity are examined by means of X-ray diffractometry. It is found out that the irradiation with gamma-quanta changes the structure of the mechanically activated powder composition. The higher irradiation dose, the higher the structure crystallinity of both components with no change in phase state. At the same time, the parameters of Ti and Al crystal lattices approach to the initial parameters observed before the mechanical activation. The irradiation with gammaquanta leads to decrease of internal stresses in the mechanically activated powder composition while nanocrystallinity of the structure remains unchanged. Using of powder compositions exposed to the irradiation with gamma-quanta for the SH-synthesis helps to increase speed of the reaction, decrease the peak firing temperature and improve homogeneity, as well as the main phase of the produced material is TiAl.

High T c layered ferrielectric crystals by coherent spinodal decomposition

DOE PAGES

Susner, Michael A.; Belianinov, Alex; Borisevich, Albina Y.; ...

2015-11-13

Research in the rapidly-developing field of 2D-electronic materials has thus far been focused on metallic and semiconducting materials. However, complementary dielectric materials such as non-linear dielectrics are needed to enable realistic device architectures. Candidate materials require tunable dielectric properties and pathways for heterostructure assembly. Here we report on a family of cation-deficient transition metal thiophosphates whose unique chemistry makes them a viable prospect for these applications. In these materials, naturally occurring ferrielectric heterostructures composed of centrosymmetric In 4/3P 2S 6 and ferrielectrically-active CuInP 2S 6 are realized by controllable chemical phase separation in van-der-Waals bonded single crystals. CuInP 2S 6more » by itself is a layered ferrielectric with Tc just over room-temperature which rapidly decreases with homogenous doping. Surprisingly, in our composite materials, the ferrielectric Tc of the polar CuInP 2S 6 phase increases. This effect is enabled by unique spinodal decomposition that retains the overall van-der-Waals layered morphology of the crystal, but chemically separates CuInP 2S 6 and In 4/3P 2S 6 within each layer. The average spatial periodicity of the distinct chemical phases can be finely controlled by altering the composition and/or synthesis conditions. One intriguing prospect for such layered spinodal alloys is large volume synthesis of 2D in-plane heterostructures with periodically alternating polar and non-polar phases.« less

Superconductivity in metastable phases of phosphorus-hydride compounds under high pressure

NASA Astrophysics Data System (ADS)

Flores Livas, Jose; Amsler, Maximilian; Sanna, Antonio; Heil, Christoph; Boeri, Lilia; Profeta, Gianni; Wolverton, Crhis; Goedecker, Stefan; Gross, E. K. U.

Recently, compressed phosphine was reported to metallize at pressures above 45 GPa, reaching a superconducting transition temperature (Tc) of 100 K at 200 GPa. However, neither the exact composition nor the crystal structure of the superconducting phase have been conclusively determined. In this work the phase diagram of PHn (n = 1 , 2 , 3 , 4 , 5 , 6) was extensively explored by means of ab initio crystal structure prediction methods. The results do not support the existence of thermodynamically stable PHn compounds, which exhibit a tendency for elemental decomposition at high pressure even when vibrational contributions to the free energies are taken into account. Although the lowest energy phases of PH1 , 2 , 3 display Tc's comparable to experiments, it remains questionable if the measured values of Tc can be fully attributed to a phase-pure compound of PHn. This work was done within the NCCR MARVEL project.

Component effects on crystallization of RE-containing aluminoborosilicate glass

NASA Astrophysics Data System (ADS)

Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

2016-09-01

Lanthanide-aluminoborosilicate (LABS) glass is one option for immobilizing rare earth (RE) oxide fission products generated during reprocessing of pyroprocessed fuel. This glass system can accommodate a high loading of RE oxides and has excellent chemical durability. The present study describes efforts to model equilibrium crystallinity as a function of glass composition and temperature as well as liquidus temperature (TL) as a function of glass composition. The experimental method for determining TL was ASTM C1720-11. Typically, three crystalline phases were formed in each glass: Ce-borosilicate (Ce3BSi2O10), mullite (Al10Si2O19), and corundum (Al2O3). Cerianite (CeO2) was a common minor crystalline phase and Nd-silicate (Nd2Si2O7) occurred in some of the glasses. In the composition region studied, TL decreased as SiO2 and B2O3 fractions increased and strongly increased with increasing fractions of RE oxides; Al2O3 had a moderate effect on the TL but, as expected, it strongly affected the precipitation of Al-containing crystals.

Solidification studies of nanocrystalline and quasicrystalline materials from the undercooled state

NASA Astrophysics Data System (ADS)

Croat, Thomas Kevin

2001-07-01

Nanocrystallization occurring during metallic glass devitrification is studied in Zr-Al-Ni-Cu bulk metallic glasses (BMGs) and Al-RE-TM (RE = rare-earth, TM = transition metal) metallic glasses. The importance of transient nucleation in BMG devitrification was established by a direct transmission electron microscopy (TEM) measurement of the grain density in two-stage annealed samples. TEM examination of low temperature annealed BMGs also suggest that amorphous phase separation is occurring prior to crystallization. Nanocrystallization of rapidly quenched Al-RE-Ni glasses was preceded by the compositional segregation of the initially homogeneous glass into Al-rich and solute-rich regions (mainly nickel-enriched) on a ≈50--100 nm length scale, suggesting amorphous phase separation. This pre-existing compositional modulation on a nanometer scale leads naturally to the development of nanocrystals. The average rare earth radius (rRE) in Al-RE-Ni alloys was altered by co-substitution of chemically similar rare earth elements. In glasses with smaller r RE, nucleation of alpha-Al occurred preferentially near the boundaries of the phase-separated regions. However, phase separation did not universally lead to alpha-Al nanocrystallization; glasses with larger rRE crystallized to metastable intermetallic phases with a 50--100 nm grain size. Kinetic analysis of the alpha-Al crystallization was performed using isothermal DSC, yielding abnormally low Avrami exponents (n = 1.0--1.5); these values were found to be consistent with the observed transformation using a model that considers the overlapping diffusion fields of the alpha-Al grains during growth within the phase separated region. Containerless solidification experiments on Ti-based quasicrystal-forming alloys have been performed using various techniques, including drop-tube solidification, electromagnetic levitation (EML) and electrostatic levitation (ESL). In Ti-Fe-Si-O, the alpha-1/1 quasicrystal approximant phase is found to nucleate directly from the liquid over the range TixFe94-xSi 4(SiO2)2 with 67 < x < 69 in EML experiments. Both the alpha-1/1 phase in Ti-Fe-Si-O and the C14 Laves phase in Ti-Zr-Ni have lower relative undercoolings than nearby crystal phases. This presumably reflects the structural similarity between these polytetrahedral phases and the undercooled liquid, which leads to smaller nucleation barriers and lower maximum undercoolings.

Optical Basicity and Nepheline Crystallization in High Alumina Glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez, Carmen P.; McCloy, John S.; Schweiger, M. J.

2011-02-25

The purpose of this study was to find compositions that increase waste loading of high-alumina wastes beyond what is currently acceptable while avoiding crystallization of nepheline (NaAlSiO4) on slow cooling. Nepheline crystallization has been shown to have a large impact on the chemical durability of high-level waste glasses. It was hypothesized that there would be some composition regions where high-alumina would not result in nepheline crystal production, compositions not currently allowed by the nepheline discriminator. Optical basicity (OB) and the nepheline discriminator (ND) are two ways of describing a given complex glass composition. This report presents the theoretical and experimentalmore » basis for these models. They are being studied together in a quadrant system as metrics to explore nepheline crystallization and chemical durability as a function of waste glass composition. These metrics were calculated for glasses with existing data and also for theoretical glasses to explore nepheline formation in Quadrant IV (passes OB metric but fails ND metric), where glasses are presumed to have good chemical durability. Several of these compositions were chosen, and glasses were made to fill poorly represented regions in Quadrant IV. To evaluate nepheline formation and chemical durability of these glasses, quantitative X-ray diffraction (XRD) analysis and the Product Consistency Test were conducted. A large amount of quantitative XRD data is collected here, both from new glasses and from glasses of previous studies that had not previously performed quantitative XRD on the phase assemblage. Appendix A critically discusses a large dataset to be considered for future quantitative studies on nepheline formation in glass. Appendix B provides a theoretical justification for choice of the oxide coefficients used to compute the OB criterion for nepheline formation.« less

Crystallization Kinetics of Barium and Strontium Aluminosilicate Glasses of Feldspar Composition

NASA Technical Reports Server (NTRS)

Hyatt, Mark J.; Bansal, Narottam P.

1994-01-01

Crystallization kinetics of BaO.Al2O3.2SiO2 (BAS) and SrO.Al2O3.2SiO2 (SAS) glasses in bulk and powder forms have been studied by non-isothermal differential scanning calorimetry (DSC). The crystal growth activation energies were evaluated to be 473 and 451 kJ/mol for bulk samples and 560 and 534 kJ/mol for powder specimens in BAS and SAS glasses, respectively. Development of crystalline phases on thermal treatments of glasses at various temperatures has been followed by powder x-ray diffraction. Powder samples crystallized at lower temperatures than the bulk and the crystallization temperature was lower for SAS glass than BAS. Crystallization in both glasses appeared to be surface nucleated. The high temperature phase hexacelsian, MAl2Si2O8 (M = Ba or Sr), crystallized first by nucleating preferentially on the glass surface. Also, monoclinic celsian does not nucleate directly in the glass, but is formed at higher temperatures from the transformation of the metastable hexagonal phase. In SAS the transformation to monoclinic celsian occurred rapidly after 1 h at 1100 C. In contrast, in BAS this transformation is sluggish and difficult and did not go to completion even after 10 h heat treatment at 1400 C. The crystal growth morphologies in the glasses have been observed by optical microscopy. Some of the physical properties of the two glasses are also reported.

High- and low-Am RE inclusion phases in a U-Np-Pu-Am-Zr alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn E.; Madden, James W.; O'Holleran, Thomas P.

2015-03-01

Structural, microstructural, and microchemical data were collected from rare-earth inclusions in an as-cast U-Pu-Zr alloy with ~3 at% Am, 2% Np, and 9% rare-earth elements (La, Ce, Pr, and Nd). Two RE phases with different concentrations of Am were identified. The composition of high-Am RE inclusions is ~2-5 at% La, 15-20 % Ce, 5-10% Pr, 25-45% Nd, 1% Np, 5-10% Pu, and 10-20% Am. Some areas also have O, although this does not appear to be an essential part of the high-Am RE phase. The inclusions have a face-centered cubic structure with a lattice parameter a ~ 0.54 nm. Themore » composition of the only low-Am RE inclusion studied in detail is ~~35-40 at% O, 40-45 % Nd, 1-2% Zr, 4-5% La, 9-10% Ce, and 6-7% Pr. This inclusion is an oxide with a crystal structure similar to the room-temperature structure of Nd 2O 3. Microstructural features suggest that oxidation occurred during casting, and that early crystallization of high-temperature oxides led to formation of two distinct RE phases.« less

Sphene-centered ocellar texture as a petrological tool to unveil the mechanism facilitating magma mixing

NASA Astrophysics Data System (ADS)

Gogoi, Bibhuti; Saikia, Ashima; Ahmad, Mansoor

2015-04-01

The sphene-centered ocellar texture is a unique magma mixing feature characterized by leucocratic ocelli of sphene enclosed in a biotite/hornblende-rich matrix (Hibbard, 1991). The ocelli usually consist of plagioclase, K-feldspar and quartz with sphene crystals at its centre. Although geochemical and isotopic data provide concrete evidence for the interaction between two compositionally distinct magmas, the exact processes by which mixing takes place is yet uncertain. So, textural analysis can be used to decipher the behaviour of two disparate magmas during mixing. Presented work is being carried out on the sphene ocelli, occurring in hybrid rocks of the Nimchak Granite Pluton (NGP), to understand its formation while two compositionally different magmas come in contact and try to equilibrate. The NGP is ca. 1 km2in extent which has been extensively intruded by number of mafic dykes exhibiting well preserved magma mixing and mingling structures and textures in the Bathani Volcano-Sedimentary Sequence (BVSS) located on the northern fringe of the Proterozoic Chotanagpur Granite Gneiss Complex (CGGC) of eastern Indian Shield. From petrographic and mineral chemical studies we infer that when basaltic magma intruded the crystallizing granite magma chamber, initially the two compositionally different magmas existed as separate entities. The first interaction that took place between the two phases is diffusion of heat from the relatively hotter mafic magma to the colder felsic one followed by diffusion of elemental components like K and incompatible elements from the felsic to the mafic domain. Once thermal equilibrium was attained between the mafic and felsic melts, the rheological contrasts between the two phases were greatly reduced. This allowed the felsic magma to back-vein into the mafic magma. The influx of back-veined felsic melt into the mafic system disrupted the equilibrium conditions in the mafic domain wherein minerals like amphibole, plagioclase and biotite were crystallizing. This led to the incongruent melting of amphibole and biotite to form liquids of sphene composition. Meanwhile, plagioclase continued to grow in the mafic-turned-hybrid system with a different composition after the advent of felsic melt as indicated by compositional zoning in plagioclase crystals. The newly produced sphene-liquid, owing to its higher affinity for felsic phase than mafic, got incorporated into the back-veining felsic melt forming a distinct liquid of its own. The felsic melt also incorporated crystallizing plagioclase grains in it from the mafic matrix. The mixture of felsic melt, sphene-liquid and plagioclase crystals flowed through the biotite, amphibole and plagioclase dominated matrix towards the low pressure zones to occupy the spherical void spaces left behind by escaping of gases/volatiles forming the sphene ocelli. Hibbard, M.J., 1991. Textural anatomy of twelve magma-mixed granitoid systems. In: Didier, J., Barbarin, B. (Eds.) Enclaves and granite petrology, 431-444.

In situ phase transformation of Laves phase from Chi-phase in Mo-containing Fe–Cr–Ni alloys

DOE PAGES

Tan, L.; Yang, Y.

2015-11-01

For an in situ phase transformation of the Chi (χ) phase to the Laves phase we observed in a Fe–Cr–Ni–Mo model alloy. The morphology, composition, and crystal structure of the χ and Laves phases, and their orientation relationship with the matrix austenite phase were investigated. The resulted Laves phase has larger lattice mismatch with the matrix phase than the χ phase, leading to the increase of local strain fields and the formation of dislocations. Moreover, this finding is helpful to understand the precipitation behavior of the intermetallic phases in the Mo-containing austenitic stainless steels.

Effect of niobium content on the microstructure and thermal properties of fluorapatite glass-ceramics.

PubMed

Denry, I L; Holloway, J A; Nakkula, R J; Walters, J D

2005-10-01

Niobium oxide has been shown to improve biocompatibility and promote bioactivity. The purpose of this study was to evaluate the effect of niobium oxide additions on the microstructure and thermal properties of fluorapatite glass-ceramics for biomedical applications. Four glass-ceramic compositions with increasing amounts of niobium oxide from 0 to 5 wt % were prepared. The glass compositions were melted at 1,525 degrees C for 3 h, quenched, ground, melted again at 1,525 degrees C for 3 h and furnace cooled. The coefficient of thermal expansion was measured by dilatometry. The crystallization behavior was evaluated by differential thermal analysis. The nature of the crystalline phases was investigated by X-ray diffraction. The microstructure was studied by SEM. In addition, the cytotoxicity of the ceramics was evaluated according to the ASTM standard F895--84. The results from X-ray diffraction analyses showed that fluorapatite was the major crystalline phase in all glass-ceramics. Differential thermal analyses revealed that fluorapatite crystallization occurred between 800 and 934 degrees C depending on the composition. The coefficient of thermal expansion varied from 7.6 to 9.4 x 10(-6)/ degrees C. The microstructure after heat treatment at 975 degrees C for 30 min consisted of submicroscopic fluorapatite crystals (200--300 nm) for all niobium-containing glass-ceramics, whereas the niobium-free glass-ceramic contained needle-shaped fluorapatite crystals, 2 microm in length. None of the glass-ceramics tested exhibited any cytotoxic activity as tested by ASTM standard F895--84. (c) 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2005.

Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization.

PubMed

Varitis, S; Kavouras, P; Pavlidou, E; Pantazopoulou, E; Vourlias, G; Chrissafis, K; Zouboulis, A I; Karakostas, Th; Komninou, Ph

2017-01-01

The vitrification process was applied for the stabilization and solidification of a rich in chromium ash that was the by-product of incineration of tannery sludge. Six different batch compositions were produced, based on silica as the glass former and sodium and calcium oxides as flux agents. As-vitrified products (monoliths) were either composed of silicate matrices with separated from the melt Eskolaite (Cr 2 O 3 ) crystallites or were homogeneous glasses (in one case). All as-vitrified products were thermally treated in order to transform them to partially crystallized, i.e. devitrified products. Devitrification is an important part of the work since studying the transformation of the initial as-vitrified products into glass-ceramics with better properties could result to stabilized products with potential added value. The devitrified products were diversified by the effective crystallization mode and separated crystal phase composition. These variations originated from differences in: (a) batch composition of the initial as-vitrified products and (b) thermal treatment conditions. In devitrified products crystallization led to the separation of Devitrite (Na 2 Ca 3 Si 6 O 16 ), Combeite (Na 4 Ca 4 Si 6 O 18 ) and Wollastonite (CaSiO 3 ) crystalline phases, while Eskolaite crystallites were not affected by thermal treatment. Leaching test results revealed that chromium was successfully stabilized inside the as-vitrified monoliths. Devitrification impairs chromium stabilization, only in the case where the initial as-vitrified product was a homogeneous glass. In all other cases, devitrification did not affect successful chromium stabilization. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of the crystallization features, atomic structure, and microstructure of chromium-doped monticellite

NASA Astrophysics Data System (ADS)

Subbotin, K. A.; Iskhakova, L. D.; Zharikov, E. V.; Lavrishchev, S. V.

2008-12-01

A series of Cr4+:CaMgSiO4 single crystals is grown using floating zone melting, and their microstructure, composition, and crystal structure are investigated. It is shown that regions with inclusions of second phases, such as forsterite, akermanite, MgO, and Ca4Mg2Si3O12, can form over the length of the sample. The composition of the single-phase regions of the single crystals varies from the stoichiometric monticellite CaMgSiO4 to the solid solution Ca(1 - x)Mg(1 + x)SiO4( x = 0.22). The Cr:(Ca0.88Mg0.12)MgSiO4 crystal is studied using X-ray diffraction. It is revealed that, in this case, the olivine-like orthorhombic crystal lattice is distorted to the monoclinic lattice with the parameters a = 6.3574(5) Å, b = 4.8164(4) Å, c = 11.0387(8) Å, β = 90.30(1)o, Z = 4, V = 337.98 Å3, and space group P21/ c. In the monoclinic lattice, the M(1) position of the initial olivine structure is split into two nonequivalent positions with the center of symmetry, which are occupied only by Mg2+ cations with the average length of the Mg-O bond R av = 2.128 Å. The overstoichiometric Mg2+ cations partially replace Ca2+ cations (in the M(2) position of the orthorhombic prastructure) with the average bond length of 2.347 Å in the [(Ca,Mg)-O6] octahedron. The average distance in SiO4 distorted tetrahedra is 1.541 Å.

Strain-induced nanostructure of Pb(Mg1/3Nb2/3)O3-PbTiO3 on SrTiO3 epitaxial thin films with low PbTiO3 concentration

NASA Astrophysics Data System (ADS)

Kiguchi, Takanori; Fan, Cangyu; Shiraishi, Takahisa; Konno, Toyohiko J.

2017-10-01

The singularity of the structure in (1 - x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-xPT) (x = 0-50 mol %) epitaxial thin films of 100 nm thickness was investigated from the viewpoint of the localized residual strain in the nanoscale. The films were deposited on SrTiO3 (STO) (001) single-crystal substrates by chemical solution deposition (CSD) using metallo-organic decomposition (MOD) solutions. X-ray and electron diffraction patterns revealed that PMN-xPT thin films included a single phase of the perovskite-type structure with the cube-on-cube orientation relationship between PMN-xPT and STO: (001)Film ∥ (001)Sub, [100]Film ∥ [100]Sub. X-ray reciprocal space maps showed an in-plane tensile strain in all the compositional ranges considered. Unit cells in the films were strained from the rhombohedral (pseudocubic) (R) phase to a lower symmetry crystal system, the monoclinic (MB) phase. The morphotropic phase boundary (MPB) that split the R and tetragonal (T) phases was observed at x = 30-35 for bulk crystals of PMN-xPT, whereas the strain suppressed the transformation from the R phase to the T phase in the films up to x = 50. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) analysis and its related local strain analysis revealed that all of the films have a bilayer morphology. The nanoscale strained layer formed only above the film/substrate semi-coherent interface. The misfit dislocations generated the localized and periodic strain fields deformed the unit cells between the dislocation cores from the R to an another type of the monoclinic (MA) phase. Thus, the singular and localized residual strains in the PMN-xPT/STO (001) epitaxial thin films affect the phase stability around the MPB composition and result in the MPB shift phenomena.

Surface phase separation, dewetting feature size, and crystal morphology in thin films of polystyrene/poly(ε-caprolactone) blend.

PubMed

Ma, Meng; He, Zhoukun; Li, Yuhan; Chen, Feng; Wang, Ke; Zhang, Qing; Deng, Hua; Fu, Qiang

2012-12-01

Thin films of polystyrene (PS)/poly(ε-caprolactone) (PCL) blends were prepared by spin-coating and characterized by tapping mode force microscopy (AFM). Effects of the relative concentration of PS in polymer solution on the surface phase separation and dewetting feature size of the blend films were systematically studied. Due to the coupling of phase separation, dewetting, and crystallization of the blend films with the evaporation of solvent during spin-coating, different size of PS islands decorated with various PCL crystal structures including spherulite-like, flat-on individual lamellae, and flat-on dendritic crystal were obtained in the blend films by changing the film composition. The average distance of PS islands was shown to increase with the relative concentration of PS in casting solution. For a given ratio of PS/PCL, the feature size of PS appeared to increase linearly with the square of PS concentration while the PCL concentration only determined the crystal morphology of the blend films with no influence on the upper PS domain features. This is explained in terms of vertical phase separation and spinodal dewetting of the PS rich layer from the underlying PCL rich layer, leading to the upper PS dewetting process and the underlying PCL crystalline process to be mutually independent. Copyright © 2012 Elsevier Inc. All rights reserved.

Calorimetric study of phase transitions in nanocomposites of quantum dots and a liquid crystal

NASA Astrophysics Data System (ADS)

Kalakonda, P.; Iannacchione, G. S.

2015-06-01

The complex specific heat is measured over a wide temperature range for the liquid crystal (LC) 4-cyano-4-octylbiphenyl (8CB) and cadmium sulfate quantum dots (QDs) composites as a function of QD concentration. The thermal scans were performed under near-equilibrium conditions for all samples having QDs weight percent (φw) from 0 to 3wt% over a wide range of temperature well above and below the two transitions in pure 8CB. Isotropic (I) to nematic (N) and nematic to smectic-A (SmA) phase transitions evolve in character and their transition temperatures offset by (∼2.3 to 2.6 K) lower for all composite samples as compared to that in pure 8CB. The enthalpy change associated with I-N phase transitions shows slightly different behavior on heating and cooling and it also shows crossover behavior at lower and higher QD content. The enthalpy change associated with N-SmA phase transitions is independent of QD loading and thermal treatment. Given the homogeneous and random distribution of QD in these nanocomposites, we interpret that these results as arising that the nematic phase imposes self-assembly on QDs to form one-dimensional arrays leading to QDs and induces net local disordering effect in LC media.

Travelling-solvent floating-zone growth of the dilutely Co-doped spin-ladder compound Sr14(Cu, Co)24O41

NASA Astrophysics Data System (ADS)

Bag, Rabindranath; Karmakar, Koushik; Singh, Surjeet

2017-01-01

We present here crystal growth of dilutely Co-doped spin-ladder compounds Sr14(Cu 1-x, Cox)24O41 (x = 0, 0.01, 0.03, 0.05, 0.1) using the Travelling Solvent Floating Zone (TSFZ) technique associated with an image furnace. We carried out detailed microstructure and compositional analysis. The microstructure of the frozen-in FZ revealed two bands: a lower band consisting of well-aligned single-crystalline stripes of the phase Sr14(Cu, Co)24O41 embedded in the eutectic mixture of composition SrO 18% and (Cu, Co)O 82%; and an upper band consisting of a criss-crossed pattern of these stripes. These analyses were also employed to determine the distribution coefficient of the dopants in Sr14Cu24O41. The distribution coefficient turned out to be close to 1, different from Sr2CuO3 reported previously where Co tend to accumulate in the molten zone. Direct access to the composition of the frozen-in zone eliminated any previous ambiguities associated with the composition of the peritectic point of Sr14Cu24O41; and also the eutectic point in the binary SrO-CuO phase diagram. The lattice parameters show an anisotropic variation upon Co-doping with parameters a and b increasing, c decreasing; and with an overall decrease of the unit cell volume. Magnetic susceptibility measurements were carried out on the pristine and the Co-doped crystals along the principal crystallographic axes. The spin susceptibility of the x = 0.01 crystal exhibits a strong anisotropy, which is in stark contrast with the isotropic behaviour of the pristine crystal. This anisotropy seems to arise from the intradimer exchange interaction as inferred from the anisotropy of the dimer contribution to the susceptibility of the Co-doped crystal. The Curie-tail in the magnetic susceptibility of Sr14(Cu 1-x, Cox)24O41 (x = 0, 0.01, 0.03, 0.05, 0.1) crystals (field applied parallel to the ladder) was found to scale with Co-doping - the scaling is employed to confirm a homogeneous distribution of Co in a x = 0.1 crystal boule.

Volcanic processes recorded by inclusions in sanidine megacrystals ejected from Quaternary Rockeskyll volcano, Eifel, Germany

NASA Astrophysics Data System (ADS)

Eilhard, Nicole; Schreuer, Jürgen; Stöckhert, Bernhard

2016-04-01

Sanidine megacrystals were ejected by a late stage explosive eruption at the Quaternary Rockeskyll volcanic complex, Eifel volcanic field, Germany. The homogeneous distribution of barium (about 1 % wt BaO equivalent to about 2 mole % celsian component) indicates that the nearly perfect single crystals must have crystallized in the Ostwald-Miers range from a huge reservoir, probably in the roof of a magma chamber. Irregularities during crystal growth caused trapping of hydrous melt inclusions, which are the objective of the present study. The inclusions show a characteristic concentric microstructure, in the following described from the sanidine host towards the inclusion center: (1) Ba is enriched by a factor of 2 to 3 in a ca. 0.01 mm wide rim, compared to the otherwise homogeneous sanidine host; (2) inwards, the continuous rim is overgrown by a thin crust of Ba enriched sanidine with irregular surface; (3) a layer of glass with a composition similar to sanidine; (4) a second, thinner layer of glass slightly reduced in Na2O and K2O, separated from the first glass layer by a sharp interface with approximately spherical shape; (5) a bubble containing a fluid phase, composed of H2O and minor CO2. This record is interpreted as follows: After crystallization of the sanidine megacrystals, a rise in temperature within the magmatic system caused some re-melting of the Ba-rich sanidine around the inclusions. Partitioning of Ba between the small included melt reservoir and the host caused formation of the Ba-rich rim (layer 1) by diffusive exchange. The onset of cooling lead to crystallization of the thin sanidine crust (layer 2). Finally, very rapid decompression and cooling during the subsequent explosive eruption caused sequential phase separation (two stages) in the remaining melt, the denser melt phase (layers 3 and 4) quenched to glass, the complementary low-density volatile-rich phase forming the central bubble. In summary, the microstructure and phase composition of the inclusions in the sanidine megacrystals recorded information on the history of the volcanic system prior to and during explosive eruption.

Floor tile glass-ceramic glaze for improvement of the resistance to surface abrasion

NASA Astrophysics Data System (ADS)

Gajek, M.; Lis, J.; Partyka, J.; Wójczyk, M.

2011-10-01

The results of research aimed at the study on frits and glass-ceramic glazes for floor tiles, based on compositions located in the primary field of cordierite crystallization within the system MgO-Al2O3-SiO2, have been presented. The results comprise investigations on the frits crystallization abilities, stability of the crystallizing phase under conditions of single-stage a fast firing cycle (time below 60 minutes) depending on their chemical composition and the influence of the nucleation agents. The influence of the nucleating agents namely TiO2, ZrO2, V2O5 on phase composition of obtained crystalline glazes, mechanical parameters and microstructure, has been examined. The strength tests proved increased mechanical resistance of crystalline glazes. Obtained glazes are characterized by high microhardness in range 6~8 GPa, as well as the increased wear resistance measured by the loss of weight below 100 mg / 55 cm2 (PN-EN ISO 10545-7). Significant increase of these parameters as compared with non-crystalline glazes, where micro-hardness values range between 5~6 GPa and the wear resistance values range from 120 to 200 mg, has been proved. Starting glasses (frits) and glazes of the ternary system MgO-SiO2-Al2O3, were examined with use of DTA, XRD and SEM methods.

Modified Bridgman-Stockbarger growth and characterization of LiInSe{sub 2} single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, P., E-mail: ramasamyp@ssn.edu.in; Magesh, M., E-mail: ramasamyp@ssn.edu.in; Arunkumar, A., E-mail: ramasamyp@ssn.edu.in

2014-04-24

The LiInSe{sub 2} polycrystalline materials were successfully synthesized from melt and temperature oscillation method. 8 mm diameter and 32 mm length single crystal was grown from Bridgman-Stockbarger method with steady ampoule rotation. Crystalline phase was confirmed by powder XRD pattern. Thermo gravimetric and differential thermal analysis confirms that the melting point of the grown crystal is 897°C. Rutherford backscattering analysis (RBS) gives the crystal composition as Li{sub 0.8}In{sub 1.16}Se{sub 2.04}. The crystalline perfection of the grown crystal was analyzed by High resolution X-ray diffraction measurements (HRXRD). The electrical properties of the grown crystal were analyzed by Hall effect measurements andmore » it confirms the n-type semiconducting nature.« less

Transparent Oxyfluoride Nano-Glass-Ceramics Doped with Pr3+ and Pr3+-Yb3+ for NIR Emission

NASA Astrophysics Data System (ADS)

Gorni, Giulio; Cosci, Alessandro; Pelli, Stefano; Pascual, Laura; Durán, Alicia; Pascual, M. J.

2016-12-01

Pr3+-Yb3+ co-doped oxyfluoride glasses and glass-ceramics (GC) containing LaF3 nanocrystals have been prepared to obtain NIR emission of Yb3+ ions upon Pr3+ excitation in the blue region of the visible spectrum. Two different compositions have been tested 0.1-0.5 Pr-Yb and 0.5-1 Pr-Yb, in addition to Pr3+ singly doped samples. The crystallization mechanism of the nano-glass-ceramics was studied by DTA revealing that it occurs from a constant number of nuclei, the crystal growth being limited by diffusion. HR-TEM demonstrated that phase separation acts as precursor for LaF3 crystallization and a detailed analysis of the chemical composition (EDXS) revealed the enrichment in RE3+ ions inside the initial phase separated droplets, from which the LaF3 crystals are formed. The RE3+ ions incorporation inside LaF3 crystals was also proved by photoluminescence measurements showing Stark splitting of the RE3+ ions energy levels in the glass-ceramic samples. Lifetimes measurements showed the existence of a better energy transfer process between Pr3+ and Yb3+ ions in the glass-ceramics compared to the as made glass, and the highest value of energy transfer efficiency is 59% and the highest theoretical quantum efficiency is 159%, obtained for glass-ceramics GC0.1-0.5 Pr-Yb treated at 620 ºC-40 h.

Discovery of a meta-stable Al-Sm phase with unknown stoichiometry using a genetic algorithm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Feng; McBrearty, Ian; Ott, R. T.

Unknown crystalline phases observed during the devitrification process of glassy metal alloys significantly limit our ability to understand and control phase selection in these systems driven far from equilibrium. Here, we report a new meta-stable Al 5Sm phase identified by simultaneously searching Al-rich compositions of the Al–Sm system, using an efficient genetic algorithm. The excellent match between calculated and experimental X-ray diffraction patterns confirms that this new phase appeared in the crystallization of melt-spun Al 90Sm 10 alloys.

Phase relations of iron and iron nickel alloys up to 300 GPa: Implications for composition and structure of the Earth's inner core

NASA Astrophysics Data System (ADS)

Kuwayama, Yasuhiro; Hirose, Kei; Sata, Nagayoshi; Ohishi, Yasuo

2008-09-01

We have investigated the phase relations of iron and iron-nickel alloys with 18 to 50 wt.% Ni up to over 300 GPa using a laser-heated diamond-anvil cell. The synchrotron X-ray diffraction measurements show the wide stability of hcp-iron up to 301 GPa and 2000 K and 319 GPa and 300 K without phase transition to dhcp, orthorhombic, or bcc phases. On the other hand, the incorporation of nickel has a remarkable effect on expanding the stability field of fcc phase. The geometry of the temperature-composition phase diagram of iron-nickel alloys suggests that the hcp-fcc-liquid triple point is located at 10 to 20 wt.% Ni at the pressure of the inner core boundary. The fcc phase could crystallize depending on the nickel and silicon contents in the Earth's core, both of which are fcc stabilizer.

Development and Characterization of Sr-Containing Glass-Ceramic Composites Based on Biogenic Hydroxyapatite

NASA Astrophysics Data System (ADS)

Kuda, Oleksii; Pinchuk, Nataliia; Bykov, Oleksandr; Tomila, Tamara; Olifan, Olena; Golovkova, Maryna

2018-05-01

Composite materials based on hydroxyapatite are widely used for bone tissue engineering. There is evidence of a positive effect of the presence of strontium in osteoplastic materials in the case of a Ca/Sr certain ratio. To examine the effect of the addition of Sr2+, a study was made by introducing it into the material composition based on biogenic hydroxyapatite and sodium borosilicate glass (50/50% wt.). The strontium was introduced into the composition in an amount of 1% wt. Composite materials were obtained at final sintering temperatures of 780 °C and a sintering time of 1 h. The effect of additions of glass phase and strontium affect changes in the crystal lattice of biogenic hydroxyapatite was investigated with the help of X-ray phase analysis, IR spectroscopy. Also the behavior of composites in vitro in physiological solution was studied.

Structural deformation of 0.74Pb(Mg1/3Nb2/3)O3-0.26PbTiO3 single crystal in 1-3 composites due to interface stresses and poling procedure optimization

NASA Astrophysics Data System (ADS)

Wang, Chunying; Sun, Enwei; Liu, Yingchun; Zhang, Rui; Yang, Bin; Cao, Wenwu

2016-09-01

Interface stresses strongly influence the functional property of 1-3 piezoelectric composites. Using the translucent nature of (1 - x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals, we have studied stress distributions and domain configuration changes during poling inside the crystal rods by polarizing light microscopy and piezoresponse force microscopy. It was found that the interface stresses due to interaction with polymeric filler led a deformed rhombohedral phase and caused incomplete poling near rod-edges. Compared with "hard" epoxy (Epotek301) filler, "soft" epoxy (Stycast) filler showed weaker impact on the crystals rods and less influence on domain configurations. We also show that high temperature poling (70 °C) can substantially improve the piezoelectric coefficient of composites filled with hard epoxy due to creeping above the glass transition Tg. Analytic stress distribution equations based on cylinder rods were modified to explain the physical principle and to predict the stress distribution for square rods case, which was verified by finite element simulation to be accurate within 5%.

A phase width for CaGaSn. Crystal structure of mixed intermetallic Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x} and SmGa{sub x}Sn{sub 3−x}, stability, geometry and electronic structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tillard, Monique, E-mail: mtillard@univ-montp2.fr

X-ray single-crystal structure has been established for new compositions in intermetallic systems of tin and gallium. Crystals were successfully obtained in alloys prepared from elements. The structure of SmGaSn{sub 2} (cubic Pm3̄m, a=4.5778(8) Å, Z=1, R1=0.012) is described with atomic disorder at all Sn/Ga positions and the structure of Ca{sub 4}Ga{sub 4.9}Sn{sub 3.1} (hexagonal, P6{sub 3}/mmc, a=4.2233(9), c=17.601(7) Å, Z=1, R1=0.062) raises an interesting question about existence of a composition domain for CaGaSn. Finally, Ca{sub 4}Ga{sub 4.9}Sn{sub 3.1} should be considered as a particular composition of Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x}, a compound assumed to exist in the range x ~more » 0−1. Partial atomic ordering characterizes the Sn/Ga puckered layers of hexagons whose geometries are analyzed and discussed comparatively with analogous arrangements in AlB{sub 2} related hexagonal compounds. The study is supported by rigid band model and DFT calculations performed for different experimental and hypothetic arrangements. - Graphical abstract: A phase width for Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x} belonging to the hexagonal YPtAs structure-type. - Highlights: • Single crystals of mixed tin gallium ternary intermetallics were obtained. • Partial ordering at metal sites and phase width are evidenced for Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x}. • Layer deviation to flatness is studied comparatively with related structures. • Geometry and stability analyses based on DFT calculations are provided.« less

Enhancement of thermoelectric figure of merit in β-Zn{sub 4}Sb{sub 3} by indium doping control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Pai-Chun, E-mail: pcwei68@gmail.com, E-mail: cheny2@phys.sinica.edu.tw; Hsu, Chia-Hao; Chang, Chung-Chieh

2015-09-21

We demonstrate the control of phase composition in Bridgman-grown β-Zn{sub 4}Sb{sub 3} crystals by indium doping, an effective way to overcome the difficulty of growing very pure β-Zn{sub 4}Sb{sub 3} thermoelectric material. The crystal structures are characterized by Rietveld refinement with synchrotron X-ray diffraction data. The results show an anisotropic lattice expansion in In-doped β-Zn{sub 4}Sb{sub 3} wherein the zinc atoms are partially substituted by indium ones at 36f site of R-3c symmetry. Through the elimination of ZnSb phase, all the three individual thermoelectric properties are simultaneously improved, i.e., increasing electrical conductivity and Seebeck coefficient while reducing thermal conductivity. Undermore » an optimal In concentration (x = 0.05), pure phase β-Zn{sub 4}Sb{sub 3} crystal can be obtained, which possesses a high figure of merit (ZT) of 1.4 at 700 K.« less

Energy efficient engine high-pressure turbine single crystal vane and blade fabrication technology report

NASA Technical Reports Server (NTRS)

Giamei, A. F.; Salkeld, R. W.; Hayes, C. W.

1981-01-01

The objective of the High-Pressure Turbine Fabrication Program was to demonstrate the application and feasibility of Pratt & Whitney Aircraft-developed two-piece, single crystal casting and bonding technology on the turbine blade and vane configurations required for the high-pressure turbine in the Energy Efficient Engine. During the first phase of the program, casting feasibility was demonstrated. Several blade and vane halves were made for the bonding trials, plus solid blades and vanes were successfully cast for materials evaluation tests. Specimens exhibited the required microstructure and chemical composition. Bonding feasibility was demonstrated in the second phase of the effort. Bonding yields of 75 percent for the vane and 30 percent for the blade were achieved, and methods for improving these yield percentages were identified. A bond process was established for PWA 1480 single crystal material which incorporated a transient liquid phase interlayer. Bond properties were substantiated and sensitivities determined. Tooling die materials were identified, and an advanced differential thermal expansion tooling concept was incorporated into the bond process.

Phase-Pure and Multiphase Ceramic Waste Forms: Microstructure Evolution and Cesium Immobilization

NASA Astrophysics Data System (ADS)

Tumurugoti, Priyatham

Efforts of this thesis are directed towards developing ceramic waste forms as a potential replacement for the conventional glass waste forms for the safe immobilization and disposal of nuclear wastes from the legacy weapons programs as well as commercial power production. The body of this work consists of two equal parts with first focused on multiphase waste form containing hollandite as major phase and the later, on single-phase hollandites for Cs incorporation. Part I: Multiphase waste forms:. Hollandite-rich multiphase waste form compositions processed by melt-solidification and spark plasma sintering (SPS) were characterized, compared, and validated for nuclear waste incorporation. Phase identification by X-ray diffraction (XRD) and electron back-scattered diffraction (EBSD) confirm hollandite as the major phase present in these samples along with perovskite, pyrochlore and zirconolite. Distribution of select elements observed by wavelength dispersive spectroscopy (WDS) maps indicate that Cs forms a secondary phase during SPS processing, which is considered undesirable. On the other hand Cs partitioned into hollandite phase in melt-processed samples. Further analysis of hollandite structure in melt-processed composition, by selected area electron diffraction (SAED), reveals ordered arrangement of tunnel ions (Ba/Cs) and vacancies, suggesting efficient Cs incorporation into the lattice. Following the microstructural analysis, the crystallization behavior of the multiphase composition during melt-processing was studied. The phase assemblage and evolution of hollandite, zirconolite, pyrochlore, and perovskite type structures during melt processing were studied using thermal analysis, in-situ XRD, and scanning electron microscopy (SEM). Samples prepared by melting followed by annealing and quenching were analyzed to determine and measure the progression of the phase assemblage. Samples were melted at 1500°C and heat-treated at crystallization temperatures of 1285°C and 1325°C corresponding to exothermic events identified from differential scanning calorimetry (DSC) measurements. Results indicate that the selected multiphase composition partially melts at 1500°C with hollandite coexisting as crystalline phase. Perovskite and zirconolite phases crystallized from the residual melt at temperatures below 1350°C. Depending on their respective thermal histories, different quenched samples were found to have different phase assemblages including phases such as perovskite, zirconolite and TiO2. Part II: Single phase waste forms. Hollandites with compositions Ba1.15-xCs2xCr 2.3Ti5.7O16 have been identified as promising lattices to host Cs. Series of compositions with 0 ≤ x ≤ 1.15 were prepared by sol-gel synthesis, characterized, and analyzed for Cs retention properties. Phase-pure hollandites adopting monoclinic symmetry (I2/m) were observed to form in the compositional range 0 ≤ x ≤ 0.4. Structural models for the compositions: x = 0, 0.15, and 0.25, were developed from Rietveld analysis of powder XRD and neutron diffraction data. Refined anisotropic displacement parameters (beta ij) for Ba and Cs ions in the hollandite tunnels indicate local disorder of Ba/Cs along the tunnel direction. In addition, weak super lattice reflections have also been observed in XRD patterns. Our data suggests the presence of supercell structures with ordered tunnel cations for the phase-pure hollandites studied. Finally, the performance of phase-pure hollandites have been evaluated qualitatively by chemical durability testing and ion-irradiation experiments. Elemental analysis of the leachants after 7-day leach tests show that Cs and Cr were extracted from the lattice together. No direct correlation between structural parameters or Cs content was observed. The simulated light-ion (He2+) and heavy-ion (Kr3+) irradiation experiments reveal that all the hollandite compositions studied undergo amorphization during alpha-decay events, and the extent of it increases with the Cs content. In summary, the present work validates melt-processing as an effective method to prepare multiphase waste forms with the desired phase assemblage. Ba1.15-xCs2xCr2.3Ti5.7O16 hollandite has been identified as an effective ceramic host for Cs immobilization and appropriate structural models for hollandites with different Cs levels have been developed. The structural information may be used to study or simulate the lattice-environment interaction.

Ab initio study of single-crystalline and polycrystalline elastic properties of Mg-substituted calcite crystals.

PubMed

Zhu, L-F; Friák, M; Lymperakis, L; Titrian, H; Aydin, U; Janus, A M; Fabritius, H-O; Ziegler, A; Nikolov, S; Hemzalová, P; Raabe, D; Neugebauer, J

2013-04-01

We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

Composition and crystal structure of N doped TiO2 film deposited at different O2 flow rate by direct current sputtering.

PubMed

Ding, Wanyu; Ju, Dongying; Chai, Weiping

2011-06-01

N doped Ti02 films were deposited by direct current pulse magnetron sputtering system at room temperature. The influence of 02 flow rate on the crystal structure of deposited films was studied by Stylus profilometer, X-ray photoelectron spectroscopy, and X-ray diffractometer. The results indicate that the 02 flow rate strongly controls the growth behavior and crystal structure of N doped Ti02 film. It is found that N element mainly exists as substitutional doped state and the chemical stiochiometry is near to TiO1.68±0.06N0.11±0.01 for all film samples. N doped Ti02 film deposited with 2 sccm (standard-state cubic centimeter per minute) 02 flow rate is amorphous structure with high growth rate, which contains both anatase phase and rutile phase crystal nucleuses. In this case, the film displays the mix-phase of anatase and rutile after annealing treatment. While N doped Ti02 film deposited with 12 cm(3)/min 02 flow rate displays anatase phase before and after annealing treatment. And it should be noticed that no TiN phase appears for all samples before and after annealing treatment. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Orientational Order in Liquid Crystal Complexes Based on Lanthanides

NASA Astrophysics Data System (ADS)

Dobrun, L. A.; Kovshik, A. P.; Ryumtsev, E. I.; Kalinkin, A. A.

2018-04-01

In this study, we have for the first time determined the degree of an orientational order S for a series of liquid-crystal complexes based on lanthanides (Eu+3, Gd+3, Tb+3, Dy+3) with the same ligand composition in the temperature range of existence of the nematic phase by using experimental refractometry results. We have also found an even-odd alternative S as number of protons in the ions complexing agent has consecutively increased. The obtained values of S have been compared with the corresponding degrees of order of the calamite organic liquid crystals.

Effects of Detergent β-Octylglucoside and Phosphate Salt Solutions on Phase Behavior of Monoolein Mesophases

PubMed Central

Khvostichenko, Daria S.; Ng, Johnathan J.D.; Perry, Sarah L.; Menon, Monisha; Kenis, Paul J.A.

2013-01-01

Using small-angle x-ray scattering (SAXS), we investigated the phase behavior of mesophases of monoolein (MO) mixed with additives commonly used for the crystallization of membrane proteins from lipidic mesophases. In particular, we examined the effect of sodium and potassium phosphate salts and the detergent β-octylglucoside (βOG) over a wide range of compositions relevant for the crystallization of membrane proteins in lipidic mesophases. We studied two types of systems: 1), ternary mixtures of MO with salt solutions above the hydration boundary; and 2), quaternary mixtures of MO with βOG and salt solutions over a wide range of hydration conditions. All quaternary mixtures showed highly regular lyotropic phase behavior with the same sequence of phases (Lα, Ia3d, and Pn3m) as MO/water mixtures at similar temperatures. The effects of additives in quaternary systems agreed qualitatively with those found in ternary mixtures in which only one additive is present. However, quantitative differences in the effects of additives on the lattice parameters of fully hydrated mesophases were found between ternary and quaternary mixtures. We discuss the implications of these findings for mechanistic investigations of membrane protein crystallization in lipidic mesophases and for studies of the suitability of precipitants for mesophase-based crystallization methods. PMID:24138861

Crystallization control for remediation of an FetO-rich CaO-SiO2-Al2O3-MgO EAF waste slag.

PubMed

Jung, Sung Suk; Sohn, Il

2014-01-01

In this work, the crystallization behavior of synthesized FetO-rich electric arc furnace (EAF) waste slags with a basicity range of 0.7 to 1.08 was investigated. Crystal growth in the melts was observed in situ using a confocal laser scanning microscope, and a delayed crystallization for higher-basicity samples was observed in the continuous cooling transformation and time temperature transformation diagrams. This result is likely due to the polymerization of the melt structure as a result of the increased number of network-forming FeO4 and AlO4 units, as suggested by Raman analysis. The complex incorporation of Al and Fe ions in the form of AlO4 and FeO4 tetrahedral units dominant in the melt structure at a higher basicity constrained the precipitation of a magnetic, nonstoichiometric, and Fe-rich MgAlFeO4 primary phase. The growth of this spinel phase caused a clear compositional separation from amorphous phase during isothermal cooling at 1473 K leading to a clear separation between the primary and amorphous phases, allowing an efficient magnetic separation of Fe compounds from the slag for effective remediation and recycling of synthesized EAF waste slags for use in higher value-added ordinary Portland cement.

Thermal Energy Transfer Through All Ceramic Restorations

DTIC Science & Technology

2016-06-01

particles, but newer generations have reduced the size and narrowed the range of particles in the matrix . This evolution in ceramics improved the...crystalline second phase. These ceramics have a lithium silicate glass matrix with approximately 70% lithium-disilicate crystal fill. The micron size and... composition category described by Giordano and McLaren are the Interpenetrating Phase Ceramics . These ceramics were developed as an alternative to the

Segmenting data sets for RIP.

PubMed

de Sanctis, Daniele; Nanao, Max H

2012-09-01

Specific radiation damage can be used for the phasing of macromolecular crystal structures. In practice, however, the optimization of the X-ray dose used to `burn' the crystal to induce specific damage can be difficult. Here, a method is presented in which a single large data set that has not been optimized in any way for radiation-damage-induced phasing (RIP) is segmented into multiple sub-data sets, which can then be used for RIP. The efficacy of this method is demonstrated using two model systems and two test systems. A method to improve the success of this type of phasing experiment by varying the composition of the two sub-data sets with respect to their separation by image number, and hence by absorbed dose, as well as their individual completeness is illustrated.

TEM study on a new Zr-(Fe, Cu) phase in furnace-cooled Zr-1.0Sn-0.3Nb-0.3Fe-0.1Cu alloy

NASA Astrophysics Data System (ADS)

Liu, Yushun; Qiu, Risheng; Luan, Baifeng; Hao, Longlong; Tan, Xinu; Tao, Boran; Zhao, Yifan; Li, Feitao; Liu, Qing

2018-06-01

A new Zr-(Fe, Cu) phase was found in furnace-cooled Zr-1.0Sn-0.3Nb-0.3Fe- 0.1Cu alloy and alloys aged at 580 °C for 10min, 2 h and 10 h. Electron diffraction experiment shows the crystal structure of this phase to be body-centered tetragonal with unit cell dimensions determined to be a = b = 6.49 Å, c = 5.37 Å. Its possible space groups have been discussed and the reason accounting for its formation is believed to be the addition of Cu according to the atom-level images. In addition, no crystal structural or chemical composition changes were observed throughout the aging process.

Structural, optical and electronic properties of indium sulfide compositions under influence of copper impurity produced by chemical method

NASA Astrophysics Data System (ADS)

Esmaili, Parisa; Kangarlou, Haleh; Savaloni, Hadi; Ghorannevis, Mahmood

Aqueous solutions with 70 °C and pH = 2.5 constant values were prepared from convenient chemical compounds to produce In2S3: Cu crystals and thin films. Crystal compositions were grown in this solution under special conditions. Micrographs showed amorphous In2S3 orange powder and transparent vitreous pieces of CuInS2 crystals. Indium sulfide films were produced using the same solution in CBD method, on the glass substrates at different [Cu/In] molar ratio concentrations. Cu+ ions by different concentration doped from copper chloride source into In2S3 films. The produced films were post-annealed at 400 °C for about 1 h. Their crystallography, phase transitions, element analysis and nanostructures were investigated by X-ray diffraction, SEM, EDAX and AFM analyses. β-In2S3 phase was dominant and by doping copper impurity, XRD results suggested the formation of CuInS2 compositions. Morphology of the films, nano-structures, grain shapes and hardness was changed. Optical reflectance was measured in the UV-VIS wavelength range by a spectrophotometer. Other optical properties and optical band gaps were calculated using Kramers-Kronig relations on reflectivity curves. Electronic properties were calculated by full potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). In this approach, generalized gradient approximation (GGA) was used for the exchange-correlation potential calculation. Band gap structures, density of states and imaginary parts of dielectric function were calculated for In2S3: Cu compositions.

Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides. Polypeptide vesicles by conformation-specific assembly. Ordered chiral macroporous hybrid silica-polypeptide composites

NASA Astrophysics Data System (ADS)

Bellomo, Enrico Giuseppe

2005-07-01

Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides . The aqueous, lyotropic liquid-crystalline phase behavior of an alpha helical polypeptide, has been studied using optical microscopy and X-ray scattering. Solutions of optically pure polypeptide were found to form cholesteric liquid crystals at volume fractions that decreased with increasing average chain length. At very high volume fractions, the formation of a hexagonal mesophase was observed. The pitch of the cholesteric phase could be varied by a mixture of enantiomeric samples, where the pitch increased as the mixture approached equimolar. The cholesteric phases could be untwisted, using either magnetic field or shear flow, into nematic phases, which relaxed into cholesterics upon removal of field or shear. We have found that the phase diagram of this polypeptide in aqueous solution parallels that of poly(gamma-benzyl glutamate) in organic solvents, thus providing a useful system for liquid-crystal applications requiring water as solvent. Polypeptide vesicles by conformation-specific assembly. We have found that block copolymers composed of polypeptide segments provide significant advantages in controlling both the function and supramolecular structure of bioinspired self-assemblies. Incorporation of the stable chain conformations found in proteins into block copolymers was found to provide an additional element of control, beyond amphiphilicity and composition that defines self-assembled architecture. The abundance of functionality present in amino acids, and the ease by which they can be incorporated into these materials, also provides a powerful mechanism to impart block copolypeptides with function. This combination of structure and function work synergistically to enable significant advantages in the preparation of therapeutic agents as well as provide insight into design of self-assemblies beginning to approach the complexity of natural structures such as virus capsids. Ordered chiral macroporous hybrid silica-polypeptide composites. The mineralization of organic templates has been investigated as an effective way to control the size and structure of inorganic frameworks. Hybrid structures incorporating polypeptide with silica have been prepared and characterized using X-ray scattering, TGA, SEM and TEM. The results support the interaction between silica and polymer to form ordered chiral macroporous structures that can be easily controlled by polymer molecular weight and volume fraction.

Ferri-magnetic order in Mn induced spinel Co3-xMnxO4 (0.1≤x≤1.0) ceramic compositions

NASA Astrophysics Data System (ADS)

Meena, P. L.; Sreenivas, K.; Singh, M. R.; Kumar, Ashok; Singh, S. P.; Kumar, Ravi

2016-04-01

We report structural and magnetic properties of spinel Co3-xMnxO4 (x=0.1-1.0) synthesized by solid state reaction technique. Rietveld refinement analysis of X-ray diffraction (XRD) data, revealed the formation of polycrystalline single phase Co3-xMnxO4 without any significant structural change in cubic crystal symmetry with Mn substitution, except change in lattice parameter. Temperature dependent magnetization data show changes in magnetic ordering temperature, indicating formation of antiferromagnetic (AFM) and ferrimagnetic (FM) phase at low Mn concentration (x≤0.3) and well-defined FM phase at high Mn concentration (x≥0.5). The isothermal magnetization records established an AFM/FM mixed phase for composition ranging 0.10.5.

The effect of low temperature thermal annealing on the magnetic properties of Heusler Ni-Mn-Sn melt-spun ribbons

NASA Astrophysics Data System (ADS)

Llamazares, J. L. Sánchez; Quintana-Nedelcos, A.; Ríos-Jara, D.; Sánchez-Valdes, C. F.; García-Fernández, T.; García, C.

2016-03-01

We report the effect of low temperature vacuum annealing (823 K; 550 °C) on the elemental chemical composition, structural phase transition temperatures, phase structure, and magnetic properties of Ni50.6Mn36.3Sn13.1 as-solidified ribbons. Their elemental chemical composition, highly oriented columnar-like microstructure and single-phase character (L21-type crystal structure for austenite) remain unchanged after this low temperature annealing. Annealed ribbons show a reduction of interatomic distances which lead to a small change in the characteristic phase transition temperatures ( 3-6 K) but to a significant rise of 73 and 63% in the saturation magnetization of the martensite and austenite phases, respectively, that can be strictly ascribed to the strengthening of ferromagnetic interactions due to the change in interatomic distances.

Titanium-bearing phases in the Earth's mantle (evidence from experiments in the MgO-SiO2-TiO2 ±Al2O3 system at 10-24 GPa)

NASA Astrophysics Data System (ADS)

Sirotkina, Ekaterina; Bobrov, Andrey; Bindi, Luca; Irifune, Tetsuo

2017-04-01

Introduction Despite significant interest of experimentalists to the study of geophysically important phase equilibria in the Earth's mantle and a huge experimental database on a number of the model and multicomponent systems, incorporation of minor elements in mantle phases was mostly studied on a qualitative level. The influence of such elements on structural peculiarities of high-pressure phases is poorly investigated, although incorporation of even small portions of them may have a certain impact on the PT-parameters of phase transformations. Titanium is one of such elements with the low bulk concentrations in the Earth's mantle (0.2 wt % TiO2) [1]; however, Ti-rich lithologies may occur in the mantle as a result of oceanic crust subduction. Thus, the titanium content is 0.6 wt% in Global Oceanic Subducted Sediments (GLOSS) [2], and 1.5 wt% TiO2, in MORB [3]. In this regard, accumulation of titanium in the Earth's mantle is related to crust-mantle interaction during the subduction of crustal material at different depths of the mantle. Experimental methods At 10-24 GPa and 1600°C, we studied the full range of the starting materials in the MgSiO3 (En) - MgTiO3 (Gkl) system in increments of 10-20 mol% Gkl and 1-3 GPa, which allowed us to plot the phase PX diagram for the system MgSiO3-MgTiO3 and synthesize titanium-bearing phases with a wide compositional range. The experiments were performed using a 2000-t Kawai-type multi-anvil high-pressure apparatus at the Geodynamics Research Center, Ehime University (Japan). The quenched samples were examined by single-crystal X-ray diffractometer, and the composition of phases was analyzed using SEM-EDS. Results The main phases obtained in experiments were rutile, wadsleyite, MgSiO3-enstatite, MgTiO3-ilmenite, MgTiSi2O7 with the weberite structure type (Web), Mg(Si,Ti)O3 and MgSiO3 with perovskite-type structure. At a pressure of 13 GPa for Ti-poor bulk compositions, an association of En+Wad+Rt is replaced by the paragenesis of Web+Wad+Rt. With increasing Glk content in the starting composition, Gkl+Wad+Rt association is formed. At a pressure of >17 GPa, an association of two phases with Prv-type structure is stable within a narrow range of starting compositions. Addition of Al to the starting material allows us to simulate the composition of natural bridgmanites, since lower mantle bridgmanites are characterized by significant Al contents. In addition, this study shows that, in contrast to Al, the high contents of Ti can stabilize bridgmanite-like compounds at considerably lower pressure (18 GPa) in comparison with pure MgSiO3 bridgmanite. Small crystals of titanium-rich phases, including Ti-Al-Brd and Web were examined by single-crystal X-ray diffractometer, which allowed us to study the influence of Ti on crystallochemical peculiarities of the mantle phases and on the phase transformations. This study was supported by the Foundation of the President of the Russian Federation for Young Ph.D. (projects no. MK 1277.2017.5 to E.A. Sirotkina) and partly supported by the Russian Foundation for Basic Research (project nos. 17-55-50062 to E.A. Sirotkina and A.V.Bobrov) [1] Ringwood, A.E. The chemical composition and origin of the Earth. In: Advances in Earth science. Hurley, P.M. (Editors), M.I.T. Press, Cambridge. 1966. P. 287-356 [2] Plank, T., Langmuir, C.H., 1998. The chemical composition of subducting sediment and its consequences for the crust and mantle. Chemical Geology 145, 325-394. [3] Wilson, M. (1989) Igneous Petrogenesis—A global tectonic approach, 466 p. Kluwer, Dordrecht.

Microstructure and mechanical properties of the NiNbZrTiAl amorphous alloys with 10 and 25 at.% Nb content.

PubMed

Czeppe, T; Ochin, P; Sypień, A; Major, L

2010-03-01

The results of investigation of two different Ni-based glasses with compositions Ni(58)Nb(10)Zr(13)Ti(12)Al(7) and Ni(58)Nb(25)Zr(8)Ti(6)Al(3) are presented. The structure of the melt spun ribbons was amorphous. The supercooled liquid range decreased and primary crystallization temperature increased with increasing Nb content while the parameter T(g)/T(m) slightly increased. The crystallization process proceeded in a different way. The ribbon containing 10 at.% Nb showed typical primary crystallization of the 50 nm grains of the NiTi(Nb) cubic phase; the ribbon containing 25 at.% of Nb revealed high thermal stability of the amorphous phase, which crystallized only in a small amount in the range of primary crystallization, preserving large fraction of the amorphous phase even high above the end of the crystallization. The tensile load-displacement curves were also different. In both cases, the ribbons revealed quite a large range of the plastic elongation. The ribbon containing 10% Nb showed stress relaxation and was maximally elongated up to 0.6. The ribbon with 25 at.% Nb revealed a hardening effect and the slightly smaller maximal elongation following it. The microstructure of the deformed specimens showed deformation bands parallel to the tensile axis, microcracks formation along shear bands and river-like pattern at the fracture surfaces. In both cases, high resolution electron microscope did not reveal any crystallization after deformation.

Effect of the synthesis conditions on the electrochemical properties of LiFePO{sub 4} obtained from NH{sub 4}FePO{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prosini, Pier Paolo, E-mail: pierpaolo.prosini@enea.it; Gislon, Paola; Cento, Cinzia

Graphical abstract: - Highlights: • Four different samples of FAP were synthesized by precipitation techniques. • The samples were used as precursors to synthesize electrochemical active LiFePO{sub 4}. • Their morphology, composition, structure and electrochemical performance were studied. • The LiFePO{sub 4} electrochemical performance resulted affected by the preparation method - Abstract: In this paper the morphological, structural and electrochemical properties of crystalline lithium iron phosphate (LiFePO{sub 4}) obtained from ferrous ammonium phosphate (FAP) have been studied. The FAP was obtained following four different processes, namely: (1) homogeneous phase precipitation, (2) heterogeneous phase precipitation from stoichiometric sodium phosphate, (3) heterogeneousmore » phase precipitation from stoichiometric ammonium phosphate, and (4) heterogeneous phase precipitation from over stoichiometric ammonium phosphate. Lithium iron phosphate was prepared by solid state reaction of FAP with lithium hydroxide. In order to evaluate the effect of reaction time and synthesis temperature the LiFePO{sub 4} was prepared varying the heating temperatures (550, 600 and 700 °C) and the reaction times (1 or 2 h). The morphology of the materials was evaluated by scanning electron microscopy while the chemical composition was determined by electron energy loss spectroscopy. X-ray diffraction was used to evaluate phase composition, crystal structure and crystallite size. The so obtained LiFePO{sub 4}'s were fully electrochemical characterized and a correlation was found between the crystal size and the electrochemical performance.« less

Analysis of holographic polymer-dispersed liquid crystals (HPDLCs) for tunable low frequency diffractive optical elements recording

NASA Astrophysics Data System (ADS)

Fernández, R.; Gallego, S.; Márquez, A.; Francés, J.; Martínez, F. J.; Pascual, I.; Beléndez, A.

2018-02-01

Holographic polymer dispersed liquid crystals (HPDLCs) are the result of the optimization of the photopolymer fabrication techniques. They are made by recording in a photopolymerization induced phase separation process (PIPS) in which the liquid crystal molecules diffuse to dark zones in the diffraction grating originated. Thanks to the addition of liquid crystal molecules to the composition, this material has a dynamic behavior by reorientation of the liquid crystal molecules applying an electrical field. In this sense, it is possible to use this material to make dynamic devices. In this work, we study the behavior of this material working in low frequencies with different spatial periods of blazed gratings, a sharp profile whose recording is possible thanks to the addition of a Holoeye LCoS-Pluto spatial light modulator with a resolution of 1920 × 1080 pixels (HD) and a pixel size of 8 × 8 μm2. This device allows us to have an accurate and dynamic control of the phase and amplitude of the recording beam.

Crystallization dynamics and interface stability of strontium titanate thin films on silicon.

PubMed

Hanzig, Florian; Hanzig, Juliane; Mehner, Erik; Richter, Carsten; Veselý, Jozef; Stöcker, Hartmut; Abendroth, Barbara; Motylenko, Mykhaylo; Klemm, Volker; Novikov, Dmitri; Meyer, Dirk C

2015-04-01

Different physical vapor deposition methods have been used to fabricate strontium titanate thin films. Within the binary phase diagram of SrO and TiO 2 the stoichiometry ranges from Ti rich to Sr rich, respectively. The crystallization of these amorphous SrTiO 3 layers is investigated by in situ grazing-incidence X-ray diffraction using synchrotron radiation. The crystallization dynamics and evolution of the lattice constants as well as crystallite sizes of the SrTiO 3 layers were determined for temperatures up to 1223 K under atmospheric conditions applying different heating rates. At approximately 473 K, crystallization of perovskite-type SrTiO 3 is initiated for Sr-rich electron beam evaporated layers, whereas Sr-depleted sputter-deposited thin films crystallize at 739 K. During annealing, a significant diffusion of Si from the substrate into the SrTiO 3 layers occurs in the case of Sr-rich composition. This leads to the formation of secondary silicate phases which are observed by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy.

Structures, phase stabilities, and electrical potentials of Li-Si battery anode materials

NASA Astrophysics Data System (ADS)

Tipton, William W.; Bealing, Clive R.; Mathew, Kiran; Hennig, Richard G.

2013-05-01

The Li-Si materials system holds promise for use as an anode in Li-ion battery applications. For this system, we determine the charge capacity, voltage profiles, and energy storage density solely by ab initio methods without any experimental input. We determine the energetics of the stable and metastable Li-Si phases likely to form during the charging and discharging of a battery. Ab initio molecular dynamics simulations are used to model the structure of amorphous Li-Si as a function of composition, and a genetic algorithm coupled to density-functional theory searches the Li-Si binary phase diagram for small-cell, metastable crystal structures. Calculations of the phonon densities of states using density-functional perturbation theory for selected structures determine the importance of vibrational, including zero-point, contributions to the free energies. The energetics and local structural motifs of these metastable Li-Si phases closely resemble those of the amorphous phases, making these small unit cell crystal phases good approximants of the amorphous phase for use in further studies. The charge capacity is estimated, and the electrical potential profiles and the energy density of Li-Si anodes are predicted. We find, in good agreement with experimental measurements, that the formation of amorphous Li-Si only slightly increases the anode potential. Additionally, the genetic algorithm identifies a previously unreported member of the Li-Si binary phase diagram with composition Li5Si2 which is stable at 0 K with respect to previously known phases. We discuss its relationship to the partially occupied Li7Si3 phase.

Self assembly of oppositely charged latex particles at oil-water interface.

PubMed

Nallamilli, Trivikram; Ragothaman, Srikanth; Basavaraj, Madivala G

2017-01-15

In this study we explore the self assembly of oppositely charged latex particles at decane water interfaces. Two spreading protocols have been proposed in this context. In the first method oppositely charged particles are mixed prior to spreading at the interface, this is called "premixed-mixtures". In the second protocol negatively charged particles are first spread at the interface at known coverage followed by spreading positively charged particles at known coverage and this is called "sequential-mixtures". In premixed mixtures depending on particle mixing ratio (composition) and total surface coverage a number of 2d structures ranging from 2d crystals, aggregate-crystal coexistence and 2d-gels are observed. A detailed phase diagram of this system has been explored. In sequential-mixtures for the first time we observed a new phase in colloidal monolayers called 2d-bi crystalline domains. These structures consisted regions of two crystal phases of oppositely charged particles separated by a one dimensional chain of alternating positive and negative particles. Phase diagram of this system has also been explored at various combinations of first spread and second spread particles. A possible mechanism leading to formation of these 2d bi crystalline structures has been discussed. A direct visualization of breakage and reformation of particle barriers separating the crystal phases has been demonstrated through videos. Effect of salt in the water sub phase and particle hydrophobicity on domain formation is also investigated. Copyright © 2016 Elsevier Inc. All rights reserved.

Strength and fatigue properties of three-step sintered dense nanocrystal hydroxyapatite bioceramics

NASA Astrophysics Data System (ADS)

Guo, Wen-Guang; Qiu, Zhi-Ye; Cui, Han; Wang, Chang-Ming; Zhang, Xiao-Jun; Lee, In-Seop; Dong, Yu-Qi; Cui, Fu-Zhai

2013-06-01

Dense hydroxyapatite (HA) ceramic is a promising material for hard tissue repair due to its unique physical properties and biologic properties. However, the brittleness and low compressive strength of traditional HA ceramics limited their applications, because previous sintering methods produced HA ceramics with crystal sizes greater than nanometer range. In this study, nano-sized HA powder was employed to fabricate dense nanocrystal HA ceramic by high pressure molding, and followed by a three-step sintering process. The phase composition, microstructure, crystal dimension and crystal shape of the sintered ceramic were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Mechanical properties of the HA ceramic were tested, and cytocompatibility was evaluated. The phase of the sintered ceramic was pure HA, and the crystal size was about 200 nm. The compressive strength and elastic modulus of the HA ceramic were comparable to human cortical bone, especially the good fatigue strength overcame brittleness of traditional sintered HA ceramics. Cell attachment experiment also demonstrated that the ceramics had a good cytocompatibility.

Purification and Crystal Growth of Lead Iodide by Physical Vapor Transport Method

NASA Technical Reports Server (NTRS)

Wright, G. W.; Cole, M.; Chen, Y.-F.; Chen, K.-T.; Chen, H.; Chattopadhyay, K.; Burger, A.

1998-01-01

Lead iodide (PbI2) is a layered compound semiconductor being developed as room temperature x- and gamma-ray detector. Compared to the more studied material, mercuric iodide, PbI2 has a higher melting temperature and no phase transition until liquid phase which are indications of better mechanical properties. In this study, the source material was purified by the zone-refining process, and the purest section was extracted from center of the the zone-refined ingot to be grown by physical vapor transport (PVT) method. The zone-refined material and as-grown crystals were characterized by optical microscopy and differential scanning calorimetry (DSC) to reveal the surface morphology, purity and stoichiometry. The results shows that both materials are near-stoichiometric composition, with the purity of the as-grown crystals higher than zone-refined materials. The resistivity of the as-grown crystal (10" Omega-cm) was derived from current-voltage (I-V) measurement, and is 10 times higher than the zone-refined materials. Detail results will be presented and discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yazdani, Ahmad, E-mail: Yazdania@modares.ac.ir; Shadrokh, Zohreh; Department of Physics, University of Shahrood, P.O. Box 316-36155, Shahrood

Highlights: • Opto-crystalline character of the composition of Cu{sub 2}S and S{sub 2}Sn was considered. • The formation Cu{sub 2}SnS{sub 3} is strongly related to phase separation at interface. • The entanglement of phases is strongly due to the chemical bond competition. • The suggested fluctuation region is approved by PL spectra. • Reconstruction and cluster formation is evident by formation of flat-spiral flowers. - Abstract: Optical character of crystal structure of the composition of two different semiconducting metallic sulfides, Cu{sub 2}S and S{sub 2}Sn, in pure phase formation of the ternary chalcogenide Cu{sub 2}SnS{sub 3} was considered. Because ofmore » the difficulties related to the phase separation at the definite Eutectic temperature for the composite formation, which is evident in optical absorption fluctuations, solvothermal synthesis in the intermediate temperature range 180–220 °C seems convenient where tetragonal crystal structure is investigated by XRD. Absorption fluctuations below E = E{sub g} were more pronounced for the lower limit case (180 °C) reflected in a sharp peak located at 1.48 eV on S1 as seen in UV-PL measurement. The characteristic behavior of the interface, resulting in the reconstruction and cluster formation due to the offset of bond rupturing displacement of atomic positions, is in favor of aggregation instead of agglomeration, which is evident by formation of small flat-spiral flowers in SEM images.« less

Reduction of Thermal Conductivity in Nanowires by Combined Engineering of Crystal Phase and Isotope Disorder.

PubMed

Mukherjee, S; Givan, U; Senz, S; de la Mata, M; Arbiol, J; Moutanabbir, O

2018-05-09

Nanowires are a versatile platform to investigate and harness phonon and thermal transport phenomena in nanoscale systems. With this perspective, we demonstrate herein the use of crystal phase and mass disorder as effective degrees of freedom to manipulate the behavior of phonons and control the flow of local heat in silicon nanowires. The investigated nanowires consist of isotopically pure and isotopically mixed nanowires bearing either a pure diamond cubic or a cubic-rhombohedral polytypic crystal phase. The nanowires with tailor-made isotopic compositions were grown using isotopically enriched silane precursors 28 SiH 4 , 29 SiH 4 , and 30 SiH 4 with purities better than 99.9%. The analysis of polytypic nanowires revealed ordered and modulated inclusions of lamellar rhombohedral silicon phases toward the center in otherwise diamond-cubic lattice with negligible interphase biaxial strain. Raman nanothermometry was employed to investigate the rate at which the local temperature of single suspended nanowires evolves in response to locally generated heat. Our analysis shows that the lattice thermal conductivity in nanowires can be tuned over a broad range by combining the effects of isotope disorder and the nature and degree of polytypism on phonon scattering. We found that the thermal conductivity can be reduced by up to ∼40% relative to that of isotopically pure nanowires, with the lowest value being recorded for the rhombohedral phase in isotopically mixed 28 Si x 30 Si 1- x nanowires with composition close to the highest mass disorder ( x ∼ 0.5). These results shed new light on the fundamentals of nanoscale thermal transport and lay the groundwork to design innovative phononic devices.

Prevention of trace and major element leaching from coal combustion products by hydrothermally-treated coal ash

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adnadjevic, B.; Popovic, A.; Mikasinovic, B.

2009-07-01

The most important structural components of coal ash obtained by coal combustion in 'Nikola Tesla A' power plant located near Belgrade (Serbia) are amorphous alumosilicate, alpha-quartz, and mullite. The phase composition of coal ash can be altered to obtain zeolite type NaA that crystallizes in a narrow crystallization field (SiO{sub 2}/Al{sub 2}O{sub 3}; Na{sub 2}O/SiO{sub 2}; H{sub 2}O/Na{sub 2}O ratios). Basic properties (crystallization degree, chemical composition, the energy of activation) of obtained zeolites were established. Coal ash extracts treated with obtained ion-exchange material showed that zeolites obtained from coal ash were able to reduce the amounts of iron, chromium, nickel,more » zinc, copper, lead, and manganese in ash extracts, thus proving its potential in preventing pollution from dump effluent waters.« less

Controllable crystal growth and fast reversible crystallization-to-amorphization in Sb2Te-TiO2 films

PubMed Central

Wang, Guoxiang; Li, Chao; Shi, Daotian; Nie, Qiuhua; Wang, Hui; Shen, Xiang; Lu, Yegang

2017-01-01

The structure evolution and crystallization processes of Sb2Te-TiO2 films have been investigated. The Sb2Te-rich nanocrystals, surrounded by TiO2 amorphous phases, are observed in the annealed Sb2Te-TiO2 composite films. The segregated domains exhibit obvious chalcogenide/TiOx interfaces, which elevate crystallization temperature, impede the grain growth and increase crystalline resistance. Compared with that in conventional Ge2Sb2Te5 film, the shorter time for onset crystallization (25 ns) and amorphization (100 ns) has been achieved in as-deposited (Sb2Te)94.7(TiO2)5.3 film under 60 mW laser irradiation. The corresponding recrystallization and re-amorphization can also be realized in the film. From Johnson-Mehl-Avrami (JMA) analysis, it is further found that the one-dimensional grain growth with controlled interface is dominant for the film during the fast phase-change process. Therefore, (Sb2Te)94.7(TiO2)5.3 film with improved crystallization mechanism is promising for high-stable and fast-speed memory applications. PMID:28397858

Novel growth techniques of group-IV based semiconductors on insulator for next-generation electronics

NASA Astrophysics Data System (ADS)

Miyao, Masanobu; Sadoh, Taizoh

2017-05-01

Recent progress in the crystal growth of group-IV-based semiconductor-on-insulators is reviewed from physical and technological viewpoints. Liquid-phase growth based on SiGe-mixing-triggered rapid-melting growth enables formation of hybrid (100) (110) (111)-orientation Ge-on-insulator (GOI) structures, which show defect-free GOI with very high carrier mobility (˜1040 cm2 V-1 s-1). Additionally, SiGe mixed-crystals with laterally uniform composition were obtained by eliminating segregation phenomena during the melt-back process. Low-temperature solid-phase growth has been explored by combining this process with ion-beam irradiation, additional doping of group-IV elements, metal induced lateral crystallization with/without electric field, and metal-induced layer exchange crystallization. These efforts have enabled crystal growth on insulators below 400 °C, achieving high carrier mobility (160-320 cm2 V-1 s-1). Moreover, orientation-controlled SiGe and Ge films on insulators have been obtained below the softening temperatures of conventional plastic films (˜300 °C). Detailed characterization provides an understanding of physical phenomena behind these crystal growth techniques. Applying these methods when fabricating next-generation electronics is also discussed.

Controllable crystal growth and fast reversible crystallization-to-amorphization in Sb2Te-TiO2 films.

PubMed

Wang, Guoxiang; Li, Chao; Shi, Daotian; Nie, Qiuhua; Wang, Hui; Shen, Xiang; Lu, Yegang

2017-04-11

The structure evolution and crystallization processes of Sb 2 Te-TiO 2 films have been investigated. The Sb 2 Te-rich nanocrystals, surrounded by TiO 2 amorphous phases, are observed in the annealed Sb 2 Te-TiO 2 composite films. The segregated domains exhibit obvious chalcogenide/TiO x interfaces, which elevate crystallization temperature, impede the grain growth and increase crystalline resistance. Compared with that in conventional Ge 2 Sb 2 Te 5 film, the shorter time for onset crystallization (25 ns) and amorphization (100 ns) has been achieved in as-deposited (Sb 2 Te) 94.7 (TiO 2 ) 5.3 film under 60 mW laser irradiation. The corresponding recrystallization and re-amorphization can also be realized in the film. From Johnson-Mehl-Avrami (JMA) analysis, it is further found that the one-dimensional grain growth with controlled interface is dominant for the film during the fast phase-change process. Therefore, (Sb 2 Te) 94.7 (TiO 2 ) 5.3 film with improved crystallization mechanism is promising for high-stable and fast-speed memory applications.

Phase transformation in rapidly quenched Fe-Cr-Co-Mo-Ti-Si-B alloys

NASA Astrophysics Data System (ADS)

Zhukov, D. G.; Shubakov, V. S.; Zhukova, E. Kh; Gorshenkov, M. V.

2018-03-01

The research results of phase transformations in Fe-24Cr-16Co-3Mo-0.2Ti-1Si-B alloys (with a boron content of 1 to 3% by mass) obtained by rapid quenching are presented. The structure formation regularities during the melt spinning and during the subsequent crystallization annealing in rapidly quenched bands of the Fe-Cr-Co-Mo-Ti-Si-B system alloys were studied. The changes in the phase composition of the rapidly quenched Fe-Cr-Co-Mo-Ti- Si-B system alloys after quenching at various quench rates and at different boron concentrations in the alloys are studied. It is shown that during crystallization from an amorphous state, at temperatures above 570 °C, in addition to the α-phase, the σ-phase appears first, followed by the γ-phase. Heat treatment of rapidly quenched bands to high-coercive state was carried out. A qualitative assessment of magnetic properties in a high-coercivity state was carried out. An evaluation of the level of magnetic properties in a high-coercivity state allows us to conclude that the application of a magnetic field during crystallization from an amorphous state leads to anisotropy of the magnetic properties, that is, an anisotropic effect of thermo-magnetic treatment is detected.

Organic alloy systems suitable for the investigation of regular binary and ternary eutectic growth

NASA Astrophysics Data System (ADS)

Sturz, L.; Witusiewicz, V. T.; Hecht, U.; Rex, S.

2004-09-01

Transparent organic alloys showing a plastic crystal phase were investigated experimentally using differential scanning calorimetry and directional solidification with respect to find a suitable model system for regular ternary eutectic growth. The temperature, enthalpy and entropy of phase transitions have been determined for a number of pure substances. A distinction of substances with and without plastic crystal phases was made from their entropy of melting. Binary phase diagrams were determined for selected plastic crystal alloys with the aim to identify eutectic reactions. Examples for lamellar and rod-like eutectic solidification microstructures in binary systems are given. The system (D)Camphor-Neopentylglycol-Succinonitrile is identified as a system that exhibits, among others, univariant and a nonvariant eutectic reaction. The ternary eutectic alloy close to the nonvariant eutectic composition solidifies with a partially faceted solid-liquid interface. However, by adding a small amount of Amino-Methyl-Propanediol (AMPD), the temperature of the nonvariant eutectic reaction and of the solid state transformation from plastic to crystalline state are shifted such, that regular eutectic growth with three distinct nonfaceted phases is observed in univariant eutectic reaction for the first time. The ternary phase diagram and examples for eutectic microstructures in the ternary and the quaternary eutectic alloy are given.

Low-temperature phase transformations in 4-cyano-4‧-pentyl-biphenyl (5CB) filled by multiwalled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lebovka, N.; Melnyk, V.; Mamunya, Ye.; Klishevich, G.; Goncharuk, A.; Pivovarova, N.

2013-08-01

The effects of multiwalled carbon nanotubes (NTs) on low-temperature phase transformations in 5CB were studied by means of differential scanning calorimetry (DSC), low-temperature photoluminescence and measurements of electrical conductivity. The concentration of NTs was varied within 0-1 wt% The experimental data, obtained for pure 5CB by DSC and measurements of photoluminescence in the heating mode, evidenced the presence of two crystallization processes at T≈229 K and T≈262 K, which correspond to C1a→C1b, and C1b→C2 phase transformations. Increase of temperature T from 10 K tо 229 K provoked the red shift of photoluminescence spectral band that was explained by flattening of 5CB molecule conformation. Moreover, the photoluminescence data allow to conclude that crystallization at T≈229 K results in conformation transition to non-planar 5CB structure characteristic to ideal crystal. The non-planar conformations were dominating in nematic phase, i.e., at T>297 K. Electrical conductivity data for 5CB-NT composites revealed supplementary anomaly inside the stable crystalline phase C2, identified earlier in the temperature range 229-296.8 K. It can reflect the influence of phase transformation of 5CB in interfacial layers on the transport of charge carriers between NTs.

Uranium distribution in pseudowollastonite slag from a phosphorus furnace

USGS Publications Warehouse

Young, Edward; Altschuler, Zalman S.

1956-01-01

Silicate slag from the Victor Chemical Company phosphorus furnace at Tarpon Springs, Fla., has been found to consist essentially of pseudowollastonite, α-CaSiO3. The first-formed crystals are euhedral laths which form a mesh making up most of the slag. As the slag continues to solidify, its composition changes slightly and more equant, subhedral crystals of pseudowollastonite are deposited within the framework of the earlier material. Finally, anherdral masses of fibrous, poorly crystallized material are deposited in the remaining pore spaces which are not always completely filled. Spherules of iron phosphide, Fe2P, occur very sparsely in the slag as inclusions from the immiscible iron phosphide melt. Uranium content increases in the later crystal products of the slag, and by heavy-liquid fractionation it has been possible to segregate partially the phases and to obtain a fourfold concentration of uranium in 5 percent of the material and a twofold concentration in 30 percent of the material. Nuclear-emulsion studies indicate that the last phases of the silicate slag are actually eight times as radioactive as the early phases. In addition, the iron phosphide spherules are comparably enriches in uranium.

PbF2-based single crystals and phase diagrams of PbF2-MF2 systems (M = Mg, Ca, Sr, Ba, Cd)

NASA Astrophysics Data System (ADS)

Buchinskaya, I. I.; Fedorov, Pavel P.; Sobolev, B. P.

1997-07-01

Optical grade single crystals of Pb0.67Cd0.33F2 and Pb1-xCaxF2 (x less than 0.05) were grown by the Bridgman technique in graphite crucibles under fluorinating atmosphere of teflon pyrolysis products. For determinations of concentration areas of solid solutions, suitable for crystal growth, the phase interactions in the systems PbF2 with fluorides of alkaline-earth elements and Cd were studied by DTA and x-ray powder diffraction techniques. Phase diagrams were described by corresponding thermodynamic models. Transition from pure PbF2 to two- component Pb0.67Cd0.33F2 crystal is accompanied by some increase in radiation hardness of the latter and positive changes of mechanical characteristics (the Pb0.67Cd0.33F2 composition microhardness is 147 plus or minus 5 kg/mm2 that is 5 times that of a pure lead fluoride, 28 plus or minus 4 kg/mm2). These solid solutions have a cubic Fm3m fluorite-type lattice as a high-temperature modification of PbF2.

A cascade of magmatic events during the assembly and eruption of a super-sized magma body

NASA Astrophysics Data System (ADS)

Allan, Aidan. S. R.; Barker, Simon J.; Millet, Marc-Alban; Morgan, Daniel J.; Rooyakkers, Shane M.; Schipper, C. Ian; Wilson, Colin J. N.

2017-07-01

We use comprehensive geochemical and petrological records from whole-rock samples, crystals, matrix glasses and melt inclusions to derive an integrated picture of the generation, accumulation and evacuation of 530 km3 of crystal-poor rhyolite in the 25.4 ka Oruanui supereruption (New Zealand). New data from plagioclase, orthopyroxene, amphibole, quartz, Fe-Ti oxides, matrix glasses, and plagioclase- and quartz-hosted melt inclusions, in samples spanning different phases of the eruption, are integrated with existing data to build a history of the magma system prior to and during eruption. A thermally and compositionally zoned, parental crystal-rich (mush) body was developed during two periods of intensive crystallisation, 70 and 10-15 kyr before the eruption. The mush top was quartz-bearing and as shallow as 3.5 km deep, and the roots quartz-free and extending to >10 km depth. Less than 600 year prior to the eruption, extraction of large volumes of 840 °C low-silica rhyolite melt with some crystal cargo (between 1 and 10%), began from this mush to form a melt-dominant (eruptible) body that eventually extended from 3.5 to 6 km depth. Crystals from all levels of the mush were entrained into the eruptible magma, as seen in mineral zonation and amphibole model pressures. Rapid translation of crystals from the mush to the eruptible magma is reflected in textural and compositional diversity in crystal cores and melt inclusion compositions, versus uniformity in the outermost rims. Prior to eruption the assembled eruptible magma body was not thermally or compositionally zoned and at temperatures of 790 °C, reflecting rapid cooling from the 840 °C low-silica rhyolite feedstock magma. A subordinate but significant volume (3-5 km3) of contrasting tholeiitic and calc-alkaline mafic material was co-erupted with the dominant rhyolite. These mafic clasts host crystals with compositions which demonstrate that there was some limited pre-eruptive physical interaction of mafic magmas with the mush and melt-dominant body. However, the mafic magmas do not appear to have triggered the eruption or controlled magmatic temperatures in the erupted rhyolite. Integration of textural and compositional data from all available crystal types, across all dominant and subordinate magmatic components, allow the history of the Oruanui magma body to be reconstructed over a wide range of temporal scales using multiple techniques. This history spans the tens of millennia required to grow the parental magma system (U-Th disequilibrium dating in zircon), through the centuries and decades required to assemble the eruptible magma body (textural and diffusion modelling in orthopyroxene), to the months, days, hours and minutes over which individual phases of the eruption occurred, identified through field observations tied to diffusion modelling in magnetite, olivine, quartz and feldspar. Tectonic processes, rather than any inherent characteristics of the magmatic system, were a principal factor acting to drive the rapid accumulation of magma and control its release episodically during the eruption. This work highlights the richness of information that can be gained by integrating multiple lines of petrologic evidence into a holistic timeline of field-verifiable processes.

Detergent-Specific Membrane Protein Crystallization Screens

NASA Technical Reports Server (NTRS)

Wiener, Michael

2007-01-01

A suite of reagents has been developed for three-dimensional crystallization of integral membranes present in solution as protein-detergent complexes (PDCs). The compositions of these reagents have been determined in part by proximity to the phase boundaries (lower consolute boundaries) of the detergents present in the PDCs. The acquisition of some of the requisite phase-boundary data and the preliminary design of several of the detergent- specific screens was supported by a NASA contract. At the time of expiration of the contract, a partial set of preliminary screens had been developed. This work has since been extended under non-NASA sponsorship, leading to near completion of a set of 20 to 30 different and unique detergent- specific 96-condition screens.

Interpretations of phenocryst embayments

NASA Astrophysics Data System (ADS)

Rust, Alison; Cashman, Katharine

2017-04-01

Phenocryst embayments in volcanic samples tend to be filled with glass, regardless of the crystallinity and vesicularly of the groundmass surrounding the phenocryst. Embayments are important in volcanology and magma petrology because: 1) they often provide the only areas of matrix glass sufficient for compositional analysis in microlite-rich samples; 2) volatile gradients in embayments are used to constrain rates of magma ascent; 3) with further crystal growth, embayments may develop into melt inclusions, an essential source of data on melt composition evolution. Robust interpretations of data from embayments requires an understanding of why they form and why vesiculation and crystallisation are locally suppressed in these melt channels during ascent. We review instabilities in crystal growth and resorption, considering latent heat, local accumulation of elements, and interaction of the crystal growth front with pre-existing bubbles and other crystals. A survey of textures in volcanic samples from several volcanoes suggests that embayment formation by growth is more common than by resorption. Crystal nucleation suppression in the embayment of a growing phenocryst can be explained by buildup of excluded elements and continued growth (rather than nucleation) of the phenocryst phase. However, the suppression of bubble formation despite the accumulation of excluded volatiles is more difficult to explain but could be related to latent heat and difficulties in bubble formation in a restricted space. Finally, we flag complications in interpretations of embayment composition data due to element accumulation and bubble nucleation suppression.

Nanomechanics of cellulose crystals and cellulose-based polymer composites

NASA Astrophysics Data System (ADS)

Pakzad, Anahita

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: - Dispersion quality and macro-mechanical properties - Nanomechanical properties at the surface and tensile properties - CNC diameter and interphase thickness. Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

Vector analysis of chemical variation in the lavas of Parícutin volcano, Mexico

USGS Publications Warehouse

Miesch, A.T.

1979-01-01

Compositional variations in the lavas of Parícutin volcano, Mexico, have been examined by an extended method of Q-mode factor analysis. Each sample composition is treated as a vector projected from an original eight-dimensional space into a vector system of three dimensions. The compositions represented by the vectors after projection are closely similar to the original compositions except for Na2Oand Fe2O3.The vectors in the three-dimensional system cluster about three different planes that represent three stages of compositional change in the Parícutin lavas. Because chemical data on the compositions of the minerals in the lavas are presently lacking, interpretations of the mineral phases that may have been involved in fractional crystallization are based on CIPW norm calculations. Changes during the first stage are attributed largely to the fractional crystallization of plagioclase and olivine. Changes during the second stage can be explained by the separation of plagioclase and pyroxene. Changes during the final stage may have resulted mostly from the assimilation of a granitic material, as previously proposed by R. E. Wilcox.

Electric, Magnetic, and Magnetoelectric Properties of Yttrium-Containing BaY0.025Ti0.9625O3-SrFe12O19 Composite

NASA Astrophysics Data System (ADS)

Rather, Mehraj ud Din; Samad, Rubiya; Want, Basharat

2018-03-01

The physical properties of BaY0.025Ti0.9625O3, SrFe12O19, and 0.90BaY0.025Ti0.9625O3-0.10 SrFe12O19 composite have been studied. The proposed composite was synthesized by solid-state reaction method from yttrium barium titanate processed by solid-state reaction and strontium hexaferrite obtained by a sol-gel process. Microstructural analysis revealed monophasic grains for yttrium barium titanate phase, while loosely packed biphasic structure was observed for the composite. Powder x-ray analysis showed that the individual phases retained their crystal structure in the composite, without formation of any new additional phase. Measurement of magnetic hysteresis loops at room temperature indicated that the magnetic parameters of the composite were diluted by the presence of the ferroelectric phase. The ferroelectric hysteresis of yttrium barium titanate confirmed the ferroelectric transition at 119°C. Meanwhile, the symmetrical ferroelectric loops observed at different fields established the ferroelectric nature of the composite. Improved dielectric properties and low dielectric losses were observed due to yttrium doping in the composite. The diffuseness of the ferroelectric transitions for the composite was confirmed by the Curie-Weiss law. Activation energy calculations revealed the charge-hopping conduction mechanism in the composite. Magnetodielectric studies confirmed that the overall magnetocapacitance in the composite exhibited combined effects of magnetoresistance and magnetoelectric coupling.

Fe-Al alloy single-crystal thin film preparation for basic magnetic measurements

NASA Astrophysics Data System (ADS)

Abe, Tatsuya; Kawai, Tetsuroh; Futamoto, Masaaki; Ohtake, Mitsuru; Inaba, Nobuyuki

2018-04-01

Fe100-xAlx (x = 0, 4, 10, 20, 30 at. %) alloy films of 40 nm thickness are prepared on MgO(001) single-crystal substrates by varying substrate temperature from room temperature to 600 °C. Single-crystal films of (001) orientation with bcc-based disordered A2 structure are obtained for the Al content range of x = 0 - 20 at. %. An ordered phase of DO3 structure is observed in Fe70Al30 films prepared at temperatures higher than 200 °C, whereas (001) oriented single-crystal films of A2 structure are obtained when prepared at room temperature. The film surface profile does not depend much on the film composition, while the surface roughness increases with increasing substrate temperature. Island-like crystals are observed for films prepared at 600°C for all compositions. Difference in lattice spacing measured parallel and perpendicular to the substrate is noted for the single-crystal thin films and it increases with increasing Al content. The lattice strain in single-crystal film is caused possibly to accommodate the lattice mismatch with the MgO substrate. The (001)-oriented single-crystal films with A2 structure show four-fold symmetries in in-plane magnetic anisotropy with the easy magnetization axis A2[100] and the hard magnetization axis A2[110], whereas the films with DO3 ordered structure show almost isotropic magnetic properties.

Synthesis of nanostructured iron oxides and new magnetic ceramics using sol-gel and SPS techniques

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Shichalin, O. O.; Belov, A. A.; Portnyagin, A. S.; Mayorov, V. Yu.; Gridasova, E. A.; Golub, A. V.; Nepomnyashii, A. S.; Tananaev, I. G.; Avramenko, V. A.

2017-02-01

The original way of synthesis of nanostructured iron oxides and based on them magnetic ceramics via sequential combination of sol-gel and SPS technologies has been suggested. High quality of nanostructured iron oxides is defined by porous structure (Sspec up to 47,3 n2/g) and by phase composition of mixed and individual crystal phases (γ-Fe2O3/Fe3O4 i α-Fe2O3), depending on synthesis conditions. High-temperature SPS consolidation of nanostructured hematite powder, resulting in magnetic ceramics of high mechanical strength (fracture strength 249 MPa) has been investigated. Peculiarities of change of phase composition and composite's microstructure in the range of SPS temperatures from 700 to 900 °C have been revealed. Magnetic properties have been studied and regularities of change of magnetization (Ms) and coercive force (Hc) values of the ceramics with respect to SPS sintering temperature have been described.

Discovery of a meta-stable Al–Sm phase with unknown stoichiometry using a genetic algorithm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Feng; McBrearty, Ian; Ott, R T

Unknown crystalline phases observed during the devitrification process of glassy metal alloys significantly limit our ability to understand and control phase selection in these systems driven far from equilibrium. Here, we report a new meta-stable Al5Sm phase identified by simultaneously searching Al-rich compositions of the Al-Sm system, using an efficient genetic algorithm. The excellent match between calculated and experimental X-ray diffraction patterns confirms that this new phase appeared in the crystallization of melt-spun Al90Sm10 alloys. Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

Substantiation of Epitaxial Growth of Diamond Crystals on the Surface of Carbide Fe3AlC0.66 Phase Nanoparticles

NASA Astrophysics Data System (ADS)

Dzevin, Ievgenij M.; Mekhed, Alexander A.

2017-03-01

Samples of Fe-Al-C alloys of varying composition were synthesized under high pressures and temperatures. From X-ray analysis data, only K-phase with usual for it average parameter of elemental lattice cell, a = 0.376 nm, carbide Fe3C and cubic diamond reflexes were present before and after cooling to the temperature of liquid nitrogen.

PVDF-based semicrystalline-amorphous blends: Phase behavior and thermomechanical properties

NASA Astrophysics Data System (ADS)

Campo, Cheryl Josephine

Poly(vinylidene fluoride) [PVDF]-based semicrystalline-amorphous blends were studied to better understand the degree to which transition temperatures and mechanical properties could be varied as a function of composition. Changes in the amorphous component, processing parameters, MW, and filler content were used to manipulate blend properties. Compositional and MW series of PVDF:poly(vinyl acetate) [PVAc] blends were prepared and characterized. Varying PVDF content led to appreciable changes in crystallinity. In contrast, the effect of composition on blend glass transition temperature, Tg, was manifested only at low PVDF contents. The effect of MWPVA, on the 30:70 PVDF:PVAc composition was manifested primarily in the materials' viscoelastic response to deformation. Ternary blends of PVDF, PVAc, and poly(methyl methacrylate) [PMMA] showed limited miscibility with both a PVAc- and PMMA-rich amorphous phase apparent in all the compositions tested. PVDF:PMMA blends on the other hand exhibited good miscibility characterized by tunable Tg values which were further exploited by varying the processing conditions in order to obtain thermomechanical properties ideal for bio-related shape memory applications. PVDF:poly(ethyl methacrylate) [PEMA] blends, despite having very broad transitions, similarly exhibited desirable transition temperatures for in vivo actuation. The effect of boron nitride (BN), short carbon fibers (SCF), and clay on blend properties was also assessed. SCF filler in 50:50 PVDF:PMMA led mainly to the formation of PVDF crystals in the alpha form, clay was observed to promote growth of the beta crystal form, and BN led to a mixture of crystal forms. BN also exhibited interesting effects in the creep behavior of this system as well as the crystallization behavior of the 50:50 PVDF:PEMA blend, suppressed kinetic crystallization competing with enhanced nucleation effect under isothermal conditions observed in the latter. Depending on the processing conditions used, SCF was found to have similar nucleation effects in the 50:50 PVDF:PMMA blend but diminished degrees of crystallinity overall. Finally, shape memory behavior of PVDF:PVAc blends as well as SCF-filled 50:50 PVDF:PMMA was characterized using single and multiple shape memory cycles. Increasing PVDF content had a negative impact on PVDF:PVAc shape memory properties while increasing stress was found to have an enhancing effect as did low SCF filler content in 50:50 PVDF:PMMA.

Formation of soft magnetic high entropy amorphous alloys composites containing in situ solid solution phase

NASA Astrophysics Data System (ADS)

Wei, Ran; Sun, Huan; Chen, Chen; Tao, Juan; Li, Fushan

2018-03-01

Fe-Co-Ni-Si-B high entropy amorphous alloys composites (HEAACs), which containing high entropy solid solution phase in amorphous matrix, show good soft magnetic properties and bending ductility even in optimal annealed state, were successfully developed by melt spinning method. The crystallization phase of the HEAACs is solid solution phase with body centered cubic (BCC) structure instead of brittle intermetallic phase. In addition, the BCC phase can transformed into face centered cubic (FCC) phase with temperature rise. Accordingly, Fe-Co-Ni-Si-B high entropy alloys (HEAs) with FCC structure and a small amount of BCC phase was prepared by copper mold casting method. The HEAs exhibit high yield strength (about 1200 MPa) and good plastic strain (about 18%). Meanwhile, soft magnetic characteristics of the HEAs are largely reserved from HEAACs. This work provides a new strategy to overcome the annealing induced brittleness of amorphous alloys and design new advanced materials with excellent comprehensive properties.

The Effect of 4-Octyldecyloxybenzoic Acid on Liquid-Crystalline Polyurethane Composites with Triple-Shape Memory and Self-Healing Properties

PubMed Central

Ban, Jianfeng; Zhu, Linjiang; Chen, Shaojun; Wang, Yiping

2016-01-01

To better understand shape memory materials and self-healing materials, a new series of liquid-crystalline shape memory polyurethane (LC-SMPU) composites, named SMPU-OOBAm, were successfully prepared by incorporating 4-octyldecyloxybenzoic acid (OOBA) into the PEG-based SMPU. The effect of OOBA on the structure, morphology, and properties of the material has been carefully investigated. The results demonstrate that SMPU-OOBAm has liquid crystalline properties, triple-shape memory properties, and self-healing properties. The incorporated OOBA promotes the crystallizability of both soft and hard segments of SMPU, and the crystallization rate of the hard segment of SMPU decreases when the OOBA-content increases. Additionally, the SMPU-OOBAm forms a two-phase separated structure (SMPU phase and OOBA phase), and it shows two-step modulus changes upon heating. Therefore, the SMPU-OOBAm exhibits triple-shape memory behavior, and the shape recovery ratio decreases with an increase in the OOBA content. Finally, SMPU-OOBAm exhibits self-healing properties. The new mechanism can be ascribed to the heating-induced “bleeding” of OOBA in the liquid crystalline state and the subsequent re-crystallization upon cooling. This successful combination of liquid crystalline properties, triple-shape memory properties, and self-healing properties make the SMPU-OOBAm composites ideal for many promising applications in smart optical devices, smart electronic devices, and smart sensors. PMID:28773914

Grazing incidence synchrotron X-ray diffraction of marbles consolidated with diammonium hydrogen phosphate treatments: non-destructive probing of buried minerals

NASA Astrophysics Data System (ADS)

Possenti, Elena; Colombo, Chiara; Conti, Claudia; Gigli, Lara; Merlini, Marco; Plaisier, Jasper Rikkert; Realini, Marco; Gatta, G. Diego

2018-05-01

Diammonium hydrogen phosphate (DAP)-based consolidating treatments react with carbonatic stones and form calcium phosphates phases, whose composition depends on the availability of free calcium ions. In this work, an innovative non-destructive approach based on grazing incidence X-ray diffraction (GIXRD) with synchrotron radiation (SR) is used to investigate DAP-treated Carrara marble specimens and to study the influence of the substrate composition on the crystallization of calcium phosphate phases. The outcomes indicate that the presence of compositional micro-heterogeneity of Carrara marble favours the formation of specific phases. Dicalcium phosphate dihydrate, a calcium phosphate with a low Ca/P molar ratio, is formed on carbonatic phases with a low Ca amount, such as dolomite grains and Mg-containing veins. Furthermore, this study highlights the potentialities of SR-GIXRD as a powerful non-destructive tool for the diagnostic of Cultural Heritage objects since it allows investigating the conservation history of stone materials and their interaction with the environment.

Sunlight-switchable light shutter fabricated using liquid crystals doped with push-pull azobenzene.

PubMed

Oh, Seung-Won; Baek, Jong-Min; Yoon, Tae-Hoon

2016-11-14

We propose a sunlight-switchable light shutter using liquid crystal/polymer composite doped with push-pull azobenzene. The proposed light shutter is switchable between the translucent and transparent states by application of an electric field or by UV irradiation. Switching by UV irradiation is based on the change of the liquid crystal (LC) clearing point by the photo-isomerization effect of push-pull azobenzene. Under sunlight, the light shutter can be switched from the translucent to the transparent state by the nematic-isotropic phase transition of the LC domains triggered by trans-cis photo-isomerization of the push-pull azobenzene molecules. When the amount of sunlight is low because of cloud cover or when there is no sunlight at sunset, the light shutter rapidly relaxes from its transparent state back to its initial translucent state by the isotropic-nematic phase transition induced by cis-trans back-isomerization of the push-pull azobenzene molecules.

Neutron and x-ray scattering study of phonon dispersion and diffuse scattering in (Na ,Bi ) Ti O3-x BaTi O3 single crystals near the morphotropic phase boundary

NASA Astrophysics Data System (ADS)

Luo, Chengtao; Bansal, Dipanshu; Li, Jiefang; Viehland, Dwight; Winn, Barry; Ren, Yang; Li, Xiaobing; Luo, Haosu; Delaire, Olivier

2017-11-01

Neutron and x-ray scattering measurements were performed on (N a1 /2B i1 /2 ) Ti O3-x at %BaTi O3 (NBT-x BT ) single crystals (x =4 , 5, 6.5, and 7.5) across the morphotropic phase boundary (MPB), as a function of both composition and temperature, and probing both structural and dynamical aspects. In addition to the known diffuse scattering pattern near the Γ points, our measurements revealed new, faint superlattice peaks, as well as an extensive diffuse scattering network, revealing a short-range ordering of polar nanoregions (PNR) with a static stacking morphology. In samples with compositions closest to the MPB, our inelastic neutron scattering investigations of the phonon dynamics showed two unusual features in the acoustic phonon branches, between the superlattice points, and between the superlattice points and Γ points, respectively. These critical elements are not present in the other compositions away from the MPB, which suggests that these features may be related to the tilt modes coupling behavior near the MPB.

Neutron and x-ray scattering study of phonon dispersion and diffuse scattering in ( Na , Bi ) Ti O 3 - x BaTi O 3 single crystals near the morphotropic phase boundary

DOE PAGES

Luo, Chengtao; Bansal, Dipanshu; Li, Jiefang; ...

2017-11-10

Neutron and x-ray scattering measurements were performed on (Na 1/2Bi 1/2)TiO 3-x at % BaTiO 3 (NBT-xBT) single crystals (x = 4, 5, 6.5, and 7.5) across the morphotropic phase boundary (MPB), as a function of both composition and temperature, and probing both structural and dynamical aspects. In addition to the known diffuse scattering pattern near the gamma points, our measurements revealed new, faint superlattice peaks, as well as an extensive diffuse scattering network, revealing a short-range ordering of polar nanoregions (PNR) with a static stacking morphology. Furthermore, in samples with compositions closest to the MPB, our inelastic neutron scatteringmore » investigations of the phonon dynamics showed two unusual features in the acoustic phonon branches, between the superlattice points, and between the superlattice points and gamma points, respectively. Finally, these critical elements are not present in the other compositions away from the MPB, which suggests that these features may be related to the tilt modes coupling behavior near the MPB.« less

Neutron and x-ray scattering study of phonon dispersion and diffuse scattering in ( Na , Bi ) Ti O 3 - x BaTi O 3 single crystals near the morphotropic phase boundary

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Chengtao; Bansal, Dipanshu; Li, Jiefang

Neutron and x-ray scattering measurements were performed on (Na 1/2Bi 1/2)TiO 3-x at % BaTiO 3 (NBT-xBT) single crystals (x = 4, 5, 6.5, and 7.5) across the morphotropic phase boundary (MPB), as a function of both composition and temperature, and probing both structural and dynamical aspects. In addition to the known diffuse scattering pattern near the gamma points, our measurements revealed new, faint superlattice peaks, as well as an extensive diffuse scattering network, revealing a short-range ordering of polar nanoregions (PNR) with a static stacking morphology. Furthermore, in samples with compositions closest to the MPB, our inelastic neutron scatteringmore » investigations of the phonon dynamics showed two unusual features in the acoustic phonon branches, between the superlattice points, and between the superlattice points and gamma points, respectively. Finally, these critical elements are not present in the other compositions away from the MPB, which suggests that these features may be related to the tilt modes coupling behavior near the MPB.« less

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

NASA Astrophysics Data System (ADS)

Benetti, Giulio; Cavaliere, Emanuele; Canteri, Adalberto; Landini, Giulia; Rossolini, Gian Maria; Pallecchi, Lucia; Chiodi, Mirco; Van Bael, Margriet J.; Winckelmans, Naomi; Bals, Sara; Gavioli, Luca

2017-03-01

Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

Nickel and cobalt distribution in the laterites of the Lomié region, south-east Cameroon

NASA Astrophysics Data System (ADS)

Yongue-Fouateu, R.; Ghogomu, R. T.; Penaye, J.; Ekodeck, G. E.; Stendal, H.; Colin, F.

2006-05-01

In the Lomié region (south-east Cameroon), strong weathering of serpentinized ultramafic rocks has produced a thick laterite cover with significant nickel and cobalt contents. The highest concentrations of these elements are located in the middle section of the laterite profiles, in the lower clay horizon, and preferentially along the slopes of the interfluves. The investigation of the composition of the laterite ores (by whole-rock analysis) and of the main components, using SEM/microprobe and XRD, reveals the presence of four main enriched facies: a non-differentiated facies, a layered smectitic facies, a quartz-rich facies and a gibbsitic nodular facies. Nickel, with generally low concentrations (less than 2% NiO), is hosted by several secondary mineral phases (goethite, Mn-oxyhydroxides and smectite locally). Cobalt is generally of higher grade (up to 0.9% CoO), and is associated with cryptocrystalline and crystallized Mn-oxyhydroxides. SEM/microprobe observations suggest that nickel and cobalt concentration in secondary minerals is due to repeated remobilization. This has also favored the formation of mineral phases, of which the best crystallized and most richly mineralized are mainly those of the asbolan-lithiophorite group. The SEM studies indicate that these mineral phases show various morphologies related to their chemical composition: poorly crystallized nipple shaped (Fe, Mn, Ni), fine cross-bedded needles (Mn, Ni) and elongated crystals (Mn, Al, Ni, Co) occur in the layered smectitic facies, while platy and needle-like forms (Mn, Al, Ni, Co) characterize the gibbsitic nodular facies. The predominantly cobaltiferous nature of the Lomié laterite ore deposit is the result of remobilizations and transformations of elements that led to the impoverishment of both the Ni-Co contents of the laterite but most importantly of Ni rather than Co.

Hydrous Na-garnet from Garnet Ridge; products of mantle metasomatism underneath the Colorado Plateau

NASA Astrophysics Data System (ADS)

Sakamaki, Kunihiko; Sato, Yuto; Ogasawara, Yoshihide

2016-12-01

This is the first report on amphibole exsolution in pyrope from the Colorado Plateau. Pyrope crystals delivered from mantle depths underneath the Colorado Plateau by kimberlitic volcanism at 30 Ma were collected at Garnet Ridge, northern Arizona. The garnet grains analyzed in this study occur as discrete crystals (without adjacent rock matrix) and are classified into two major groups, Cr-rich pyrope and Cr-poor pyrope. The Cr-poor pyrope group is divided into four subgroups based on exsolved phases: amphibole lamella type, ilmenite lamella type, dense lamellae type, and clinopyroxene/amphibole lamellae type. Exsolved amphibole occurs in amphibole lamella type, dense lamellae type, and clinopyroxene/amphibole lamellae type of Cr-poor pyrope. The amphibole crystals tend to have preferred orientations in their garnet hosts and occur as monomineralic hexagonal or rhombic prisms and tablets, and as multimineralic needles or blades with other exsolved phases. Exsolved amphibole has pargasitic compositions (Na2O up to 1.6 apfu based on 23 oxygen). Garnet host crystals that have undergone amphibole exsolution have low OH contents (2-42 ppmw H2O) compared to garnets that do not have amphibole lamellae (up to 115 ppmw H2O). The low OH contents of garnets hosting amphibole lamellae suggest loss of OH from garnet during amphibole exsolution. Amphibole exsolution from pyrope resulted from breakdown of a precursor "hydrous Na-garnet" composition (Mg,Na+ x)3(Al2 - x, Mgx)2Si3O12 - 2x(OH)2x. Exsolution of amphibole and other phases probably occurred during exhumation to depths shallower than 100 km prior to volcanic eruption.

Differential Thermal Analysis of Hg(1-x)Mn(x)Te Alloys in the X=0 to 0.3 Range

NASA Technical Reports Server (NTRS)

Price, M. W.; Scripa, R. N.; Szofran, F. R.; Lehoczky, S. L.; Su, C-H

1998-01-01

Understanding the experimental conditions necessary for the development of radial and axial compositional homogeneity in directionally solidified Hg(0.89)Mn(0.11)Te(MMT) crystals has been difficult due to the lack of segregation coefficient data on the Hg(1-x)Mn(x)Te alloy system in the X = 0 to 0.3 composition range. Determining segregation coefficient data from the available Hg(1-x)Mn(x)Te alloy phase equilibria data is not practical due to discrepancies in the shape of the reported solidus and liquidus curves in the X = 0 to 0.3 range. To resolve these discrepancies and to obtain segregation coefficient data which can be used to understand homogeneity in directionally solidified MMT crystals, the solidus and liquidus temperatures of seven Hg(1-x)Mn(x)Te alloys in the X = 0 to 0.3 range were determined using differential thermal analysis (DTA). The Hg(1-x)Mn(x)Te phase diagram constructed for the X = 0 to 0.3 range of this alloy system from the DTA measurements clarifies the shape of the solidus and liquidus curves in this range. The segregation coefficient for the Hg(1-x)Mn(x)Te system was found to vary from 5 to 4.4 as the solidus composition increased from 0-30 atomic percent MnTe. This information will be useful in the analysis of axial and radial homogeneity of directionally solidified MMT crystals.

Superconducting Bi1.5Pb0.5Sr2Ca2Cu3O(x) ceramics by rapid melt quenching and glass crystallization

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1989-01-01

A glass of nominal Bi(1.5)Pb(0.5)Sr2Ca2Cu3O(x) composition, prepared by rapid quenching of the melt, showed a glass transition temperature of 383 C, crystallization temperature of 446 C, melting temperature of 855 C, and bulk density of 5.69 g/cu cm in air. The activation energy for crystallization of the glass was estimated to be 292kJ/mol from non-isothermal DSC. On heating in oxygen, the glass showed a slow and continuous weight gain starting at approximately 530 C which reached a plateau at approximately 820 C. The weight gained during heating was retained on cooling to ambient conditions indicating an irreversible oxidation step. The influence of annealing conditions on the formation of various phases in the glass has been investigated. The Bi(2)Sr(2)Ca(0)Cu(1)O(6) phase crystallized out first followed by formation of other phases at higher temperatures. The high-T(sub c) phase, isostructural with Bi(2)Sr(2)Ca(2)Cu(3)O(10) was not detected below 840 C, but its fraction increased with the annealing time at 840 C. A sample annealed at 840 C for 243h in air and furnace cooled showed the highest T(sub c)(R=0) of 107.2K and a narrow transition width, delta T(sub c)(10 to 90 percent), of approximately 2 K. The high T(sub c) phase does not seem to crystallize out directly from the glass but is rather produced at high temperature by reaction between the phases formed at lower temperatures. The kinetics of 110K phase formation was sluggish. It appears that the presence of lead helps in the formation and/or stabilization of the 110 K phase.

Antiferroelectric-ferroelectric phase transition in lead zinc niobate modified lead zirconate ceramics: crystal studies, microstructure, thermal and electrical properties

NASA Astrophysics Data System (ADS)

Sukkha, Usa; Muanghlua, Rangson; Niemcharoen, Surasak; Boonchoma, Banjong; Vittayakorn, Naratip

2010-08-01

The combination of antiferroelectric PbZrO3 (PZ) and relaxor ferroelectric Pb(Zn1/3Nb2/3)O3 was prepared via the columbite precursor method. The basic characterizations were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), linear thermal expansion, differential scanning calorimetry (DSC) techniques, dielectric spectroscopy, and hysteresis measurement. The XRD result indicated that the solid solubility limit of the (1- x)PZ- xPZN system was about x=0.40. The crystal structure of (1- x)PZ- xPZN transformed from orthorhombic to rhombohedral symmetry when the concentration of PZN was increased. A ferroelectric intermediate phase began to appear between the paraelectric and antiferroelectric phases of pure PZ, with increasing PZN content. In addition, the temperature range of the ferroelectric phase increased with increasing PZN concentration. The morphotropic phase boundary (MPB) in this system was located close to the composition, x=0.20.

a Facile Synthesis of Fully Porous Tazo Composite and its Remarkable Gas Sensitive Performance

NASA Astrophysics Data System (ADS)

Liang, Dongdong; Liu, Shimin; Wang, Zhinuo; Guo, Yu; Jiang, Weiwei; Liu, Chaoqian; Ding, Wanyu; Wang, Hualin; Wang, Nan; Zhang, Zhihua

The composite of a nanocrystalline SnO2 thick film deposited on an Al-doped ZnO ceramic substrate was firstly proposed. This study also provided a simple, fast and cost effective method to prepare SnO2 thick film and Al-doped ZnO ceramic as well as the final composite. The crystal structure, morphology, composition, pore size distribution and gas sensitivity of the composite were investigated by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, Barrett-Joyner-Halenda analysis and gas sensitive measurement system. Results indicated that the composite was fully porous consisted of SnO2, ZnO and ZnAl2O4 crystal phases. The macrosized pores generated in the composite could enhance the gas infiltration into the sensing layers effectively. In this way, combining a high gas-transporting-capability and a nanocrystalline SnO2 thick film, the composite showed very impressive performance. The gas sensitivity of the composite was high enough for ethanol vapor with different concentrations, which was comparable to other kinds of reported SnO2 gas sensors, while showing two straight lines with a turning point at 1000ppm. Finally, the gas sensitive mechanism was proposed based on the microstructure and composition of the composite.

Nial and Nial-Based Composites Directionally Solidified by a Containerless Zone Process. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Joslin, Steven M.

1995-01-01

A containerless electromagnetically levitated zone (CELZ) process has been used to directionally solidify NiAl and NiAl-based composites. The CELZ processing results in single crystal NiAl (HP-NiAl) having higher purity than commercially pure NiAl grown by a modified Bridgman process (CP-NiAl). The mechanical properties, specifically fracture toughness and creep strength, of the HP-NiAl are superior to binary CP-NiAl and are used as a base-line for comparison with the composite materials subsequently studied. Two-phase composite materials (NiAl-based eutectic alloys) show improvement in room temperature fracture toughness and 1200 to 1400 K creep strength over that of binary HP-NiAl. Metallic phase reinforcements produce the greatest improvement in fracture toughness, while intermetallic reinforcement produces the largest improvement in high temperature strength. Three-phase eutectic alloys and composite materials were identified and directionally solidified with the intent to combine the improvements observed in the two-phase alloys into one alloy. The room temperature fracture toughness and high temperature strength (in air) serve as the basis for comparison between all of the alloys. Finally, the composite materials are discussed in terms of dominant fracture mechanism observed by fractography.

Crystal structure and thermal expansion of CsCaI3:Eu and CsSrBr3:Eu scintillators

NASA Astrophysics Data System (ADS)

Loyd, Matthew; Lindsey, Adam; Patel, Maulik; Koschan, Merry; Melcher, Charles L.; Zhuravleva, Mariya

2018-01-01

The distorted-perovskite scintillator materials CsCaI3:Eu and CsSrBr3:Eu prepared as single crystals have shown promising potential for use in radiation detection applications requiring a high light yield and excellent energy resolution. We present a study using high temperature powder X-ray diffraction experiments to examine a deleterious high temperature phase transition. High temperature phases were identified through sequential diffraction pattern Rietveld refinement in GSAS II. We report the linear coefficients of thermal expansion for both high and low temperature phases of each compound. Thermal expansion for both compositions is greatest in the [0 0 1] direction. As a result, Bridgman growth utilizing a seed oriented with the [0 0 1] along the growth direction should be used to mitigate thermal stress.

Self-Consistency of the Lauritzen-Hoffman and Strobl Models of Polymer Crystallization Evaluated for Poly(epsilon-caprolactone) Fractions and Effect of Composition on the Phenomenon of Concurrent Crystallization in Polyethylene Blends

NASA Astrophysics Data System (ADS)

Sheth, Swapnil Suhas

Narrow molecular weight fractions of poly(epsilon-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard- DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl's model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in .. .. iv blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m- LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization.

Surface Hardening of Composite Material by the Centrifugal-Casting Method

NASA Astrophysics Data System (ADS)

Eidelman, E. D.; Durnev, M. A.

2018-04-01

The effect of rotation flow emerging under centrifugal casting on the first-order phase transition, i.e., crystallization, has been studied using the example of producing a gradient composite material of AK12 aluminum alloy in a mixture with basalt fibers. It has been shown that a material with a hardened surface can be created. Distribution of admixtures in the main material when there is macroscopic motion has been found.

Chemical Composition Analysis and Product Consistency Tests of the ORP Phase 5 Nepheline Study Glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fox, K. M.; Edwards, T. B.; Caldwell, M. E.

In this report, the Savannah River National Laboratory (SRNL) provides chemical analyses and Product Consistency Test (PCT) results for a series of simulated high-level waste glass compositions fabricated by the Pacific Northwest National Laboratory (PNNL). These data will be used in the development of improved models for the prediction of nepheline crystallization in support of the Hanford Tank Waste Treatment and Immobilization Plant (WTP).

Effects of germanium and nitrogen incorporation on crystallization of N-doped Ge2+xSb2Te5 (x = 0,1) thin films for phase-change memory

NASA Astrophysics Data System (ADS)

Cheng, Limin; Wu, Liangcai; Song, Zhitang; Rao, Feng; Peng, Cheng; Yao, Dongning; Liu, Bo; Xu, Ling

2013-01-01

The phase-change behavior and microstructure changes of N-doped Ge3Sb2Te5 [N-GST(3/2/5)] and Ge2Sb2Te5 [GST(2/2/5)] films during the phase transition from an amorphous to a crystalline phase were studied using in situ temperature-dependent sheet resistance measurements, X-ray diffraction, and transmission electron microscopy. The optical band gaps of N-GST(3/2/5) films are higher than that of GST(2/2/5) film in both the amorphous and face-centered-cubic (fcc) phases. Ge nitride formation by X-ray photoelectron spectroscopy analysis increased the optical band gap and suppressed crystalline grain growth, resulting in an increase in the crystallization temperature and resistance in the fcc phase. As a result, the Ge- and N-doped GST(2/2/5) composite films can be considered as a promising material for phase-change memory application because of improved thermal stability and reduced power consumption.

Crystallization of Skeletal Diamonds from Graphite and Natural Coal in Presence of Hydrous Fluids at P=8 GPa and T=1400-1500° C

NASA Astrophysics Data System (ADS)

Dobrzhinetskaya, L. F.; Renfro, A. P.; Green, H. W.

2001-12-01

Most metamorphic microdiamonds from crustal UHP rocks of the Kokchetav massive, Kazakhstan are characterized by skeletal-hopper crystals, cuboid-like crystals with cavities "healed over" by graphite, rose-like crystals, and other imperfect morphologies. According to the classical theory of crystal growth at thermodynamic equilibrium, only shapes with a minimum surface energy are stable. Thus imperfect crystallographic forms of most metamorphic diamonds formally may be interpreted as metastable while the presence of other high pressure phases associated with diamond indicates that the rocks have been subjected to UHP metamorphism within the diamond stability field. The classical theory also says that a skeletal-hopper crystal is one that develops under conditions of rapid growth, a high degree of supersaturation and in the presence of impurities. In contrast to these observations, most experiments on diamond synthesis at high P (5-7.7 GPa) and T (1250 - 1900° C) from graphite (Wang et al., 1999; Hong et al., 1999; Yamaoka et al., 2000) and carbonate material (Pal'anov et al., 1999; Sokol et al.,2000) in presence of fluid phase produced perfect octahedral and cube-octahedral diamond crystals. Advanced analytical research on metamorphic diamonds and their inclusions has demonstrated that they were crystallized from a multicomponent COH-rich supercritical fluid phase, the composition of which suggests intermixture of crustal and mantle components (de Corte et al., 1999; Dobrzhinetskaya et al., 2001, Stockhert et al., 2001). We have recently synthesized imperfect diamond crystals (skeletal-hopper morphologies with effect of etching of the diamond surfaces) from graphite and natural coal + 2% Mg(OH)2 as a source for fluid phase. Conditions of experiments are: P=8-8.5 GPa, T=1400-1500° C, t=14 to 136 hours. Our experimental data are in a good agreement with similar experiments conducted by Kanda et al. (1984) who showed that with increasing water content of the system, the morphology of diamond crystals changes progressively from octahedra to crystals with elements of dodecahedra to hollow/hopper and skeletal morphologies. We hypothesize that imperfect morphologies of metamorphic diamonds are due to the presence of OH in the system.

Synthesis of three-dimensional reduced graphene oxide layer supported cobalt nanocrystals and their high catalytic activity in F-T CO2 hydrogenation

NASA Astrophysics Data System (ADS)

He, Fei; Niu, Na; Qu, Fengyu; Wei, Shuquan; Chen, Yujin; Gai, Shili; Gao, Peng; Wang, Yan; Yang, Piaoping

2013-08-01

The reduced graphene oxide (rGO) supported cobalt nanocrystals have been synthesized through an in situ crystal growth method using Co(acac)2 under solvothermal conditions by using DMF as the solvent. By carefully controlling the reaction temperature, the phase transition of the cobalt nanocrystals from the cubic phase to the hexagonal phase has been achieved. Moreover, the microscopic structure and morphology as well as the reduction process of the composite have been investigated in detail. It is found that oxygen-containing functional groups on the graphene oxide (GO) can greatly influence the formation process of the Co nanocrystals by binding the Co2+ cations dissociated from the Co(acac)2 in the initial reaction solution at 220 °C, leading to the 3D reticular structure of the composite. Furthermore, this is the first attempt to use a Co/rGO composite as the catalyst in the F-T CO2 hydrogenation process. The catalysis testing results reveal that the as-synthesized 3D structured composite exhibits ideal catalytic activity and good stability, which may greatly extend the scope of applications for this kind of graphene-based metal hybrid material.The reduced graphene oxide (rGO) supported cobalt nanocrystals have been synthesized through an in situ crystal growth method using Co(acac)2 under solvothermal conditions by using DMF as the solvent. By carefully controlling the reaction temperature, the phase transition of the cobalt nanocrystals from the cubic phase to the hexagonal phase has been achieved. Moreover, the microscopic structure and morphology as well as the reduction process of the composite have been investigated in detail. It is found that oxygen-containing functional groups on the graphene oxide (GO) can greatly influence the formation process of the Co nanocrystals by binding the Co2+ cations dissociated from the Co(acac)2 in the initial reaction solution at 220 °C, leading to the 3D reticular structure of the composite. Furthermore, this is the first attempt to use a Co/rGO composite as the catalyst in the F-T CO2 hydrogenation process. The catalysis testing results reveal that the as-synthesized 3D structured composite exhibits ideal catalytic activity and good stability, which may greatly extend the scope of applications for this kind of graphene-based metal hybrid material. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03038e

Effect of metallic silver nanoparticles on the alignment and relaxation behaviour of liquid crystalline material in smectic C* phase

NASA Astrophysics Data System (ADS)

Vimal, Tripti; Kumar Gupta, Swadesh; Katiyar, Rohit; Srivastava, Atul; Czerwinski, Michal; Krup, Katarzyna; Kumar, Sandeep; Manohar, Rajiv

2017-09-01

The influence of silver nanoparticles dispersed in a Ferroelectric Liquid Crystal (FLC) on the properties of the resultant composite system has been investigated by thermal, electro-optical, and dielectric methods. We show that the concentration of thiol capped silver nanoparticles is a critical factor in governing the alignment of nanoparticles (NPs) in the host FLC. The orientation of NPs in composite samples affects the ordering of the LC (Liquid Crystal) phase and consequently changes the various phase transition temperatures of the host LC. Formation of self-assembled 2D (two dimensional) arrays of nanoparticles is observed for high concentration of dopant in the LC, oriented perpendicular to the direction of rubbing. We propose that the molecular interaction between the thiol capped NPs and LC molecules is the key factor behind such an arrangement of NPs. Orientation of NPs has affected the relaxation behaviour and various other material parameters, significantly. A noteworthy change in DC conductivity articulates our proposed idea of the formation of 2D array of NPs perpendicular to the direction of rubbing. This comprehensive study endorses the importance of dopant concentration in modifying the properties of the host LC material.

Mössbauer study of Cu1-xZnxFe2O4 catalytic materials

NASA Astrophysics Data System (ADS)

Koleva, K.; Velinov, N.; Tsoncheva, T.; Mitov, I.

2014-04-01

Copper zinc ferrites (Cu1-xZnxFe2O4) with different composition (x = 1; 0.2; 0.5; 0.8) were prepared by conventional thermal method. Formation of well crystallized ferrite phase with cubic structure and crystallites size of about 19.08-24.39 nm was observed by Powder X-ray diffraction and Mössbauer spectroscopy. The ferrite materials were tested as catalysts in methanol decomposition to CO and H2. A strong dependence of the catalytic behaviour of Cu1-xZnxFe2O4 ferrites of their composition and the phase transformations which occurred under the reaction medium was established.

The origin of chondrules - Experimental investigation of metastable liquids in the system Mg2SiO4-SiO2

NASA Technical Reports Server (NTRS)

Blander, M.; Planner, H. N.; Keil, K.; Nelson, L. S.; Richardson, N. L.

1976-01-01

Laser-melted magnesium silicate droplets were supercooled 400-750 C below their equilibrium liquidus temperatures before crystallization and their texture was compared with that of meteoritic and lunar chondrules. Crystal morphology, width and texture were studied in relation to nucleation temperature and bulk composition. It was found that the only phase to nucleate from the forsterite-enstatite normative melts was forsterite. Highly siliceous glass, about 65% SiO2 by weight, was identified interstitially to the forsterite crystals in seven of the MgSiO4 spherules and was thought to be present in all.

A Groundmass Composition for EET 79001A Using a Novel Microprobe Technique for Estimating Bulk Compositions. Lithology A as an Impact Melt?

NASA Technical Reports Server (NTRS)

Jones, John H.; Hanson, B. Z.

2011-01-01

Petrologic investigation of the shergottites has been hampered by the fact that most of these meteorites are partial cumulates. Two lines of inquiry have been used to evaluate the compositions of parental liquids: (i) perform melting experiments at different pressures and temperatures until the compositions of cumulate crystal cores are reproduced [e.g., 1]; and (ii) use point-counting techniques to reconstruct the compositions of intercumulus liquids [e.g., 2]. The second of these methods is hampered by the approximate nature of the technique. In effect, element maps are used to construct mineral modes; and average mineral compositions are then converted into bulk compositions. This method works well when the mineral phases are homogeneous [3]. However, when minerals are zoned, with narrow rims contributing disproportionately to the mineral volume, this method becomes problematic. Decisions need to be made about the average composition of the various zones within crystals. And, further, the proportions of those zones also need to be defined. We have developed a new microprobe technique to see whether the point-count method of determining intercumulus liquid composition is realistic. In our technique, the approximating decisions of earlier methods are unnecessary because each pixel of our x-ray maps is turned into a complete eleven-element quantitative analysis. The success or failure of our technique can then be determined by experimentation. As discussed earlier, experiments on our point-count composition can then be used to see whether experimental liquidus phases successfully reproduce natural mineral compositions. Regardless of our ultimate outcome in retrieving shergottite parent liquids, we believe our pixel-bypixel analysis technique represents a giant step forward in documenting thin-section modes and compositions. For a third time, we have analyzed the groundmass composition of EET 79001, 68 [Eg]. The first estimate of Eg was made by [4] and later modified by [5], to take phase diagram considerations into account. The Eg composition of [4] was too olivine normative to be the true Eg composition, because the ,68 groundmass contains no forsteritic olivine. A later mapping by [2] basically reconfirmed the modifications of [5]. However, even the modified composition of [5] has olivine on the liquidus for 50 C before low-Ca pyroxene appears [6].

Magnetostriction and corrosion studies in single crystals of iron-gallium alloys

NASA Astrophysics Data System (ADS)

Jayaraman, Tanjore V.

Iron-gallium alloys have an excellent combination of large low-field magnetostriction, good mechanical properties, low hysteresis, and relatively low cost. This dissertation focuses on the magneto striction and corrosion behaviors of single crystals of Fe-Ga alloys. In the first part, the variation of magnetostrictive coefficient: (3/2) lambda100, with composition and heat treatment conditions of Fe-Ga alloys, is examined. Single crystals with compositions Fe-15 at.% Ga, Fe-20 at.% Ga, and Fe-27.5 at.% Ga were obtained by (a) vertical Bridgman technique (DG) and (b) vertical Bridgman technique followed by long-term annealing (LTA) and quenching. Rapid quenching from a phase region improves the (3/2) lambda 100 value in these alloys. X-ray diffraction characterization showed for the first time the direct evidence of short-range ordering in these alloys. The second part reports the first study of alpha" ordering heat treatment on the elastic properties and magnetostriction of Fe-27.5 at.% Ga alloy single crystals. The elastic constants were measured using resonant ultrasound spectroscopy (RUS), and the elastic properties and magneto-elastic coupling constant were calculated. The (3/2) lambda100 and B1 values obtained for a phase were higher than alpha" phase. The third part examines the first study of corrosion behavior of as-cast FeGa and Fe-Ga-Al alloys in acidic, basic, and simulated seawater environments. Corrosion measurements were performed by Tafel scan and polarization resistance method and in general exhibited good corrosion resistance. The fourth part examines the first study of corrosion behavior of Fe-15 at.% Ga, Fe-20 at.% Ga, and Fe-27.5 at.% Ga DG and LTA alloy single crystals and the dependence of corrosion rates on the crystal orientations. The corrosion resistance was better in basic environments followed by simulated seawater and acidic environments. The fifth part examines the effect of magnetostriction on the corrosion behavior of [100]-oriented single crystal of Fe-20 at.% Ga alloy in acidic and simulated seawater solution, first study ever of this kind. Magnetostrictive strain introduced on the application of saturation magnetic field increased the corrosion rate of [100]-oriented Fe-20 at.% Ga alloy single crystal by 40% in 0.1M HCl and decreased the corrosion rate by 15% in 3.5 wt.% NaCl solution.

Effect of sulfate ions on the crystallization and photocatalytic activity of TiO2/diatomite composite photocatalyst

NASA Astrophysics Data System (ADS)

Zhang, Jinjun; Wang, Xiaoyan; Wang, Jimei; Wang, Jing; Ji, Zhijiang

2016-01-01

TiO2 nanoparticles were immobilized on diatomite by hydrolysis-deposition method using titanium tetrachloride as precursor. The effect of sulfate ions on the crystallization and photocatalytic activity of TiO2/diatomite composite photocatalyst was characterized by TG-DSC, XRD, BET surface area, SEM, FT-IR spectroscopy, XPS and UV-vis diffuse reflectance spectra. The results indicate that addition of a small amount of sulfate ions promotes the formation of anatase phase and inhibits the transformation from anatase to rutile. On the other hand, sulfate ions immobilized on the surface of TiO2/diatomite have strong affinity for electrons, capturing the photo-generated electrons, which hinders the recombination of electrons and holes.

The Deep Crust Magmatic Refinery, Part 1: A Coupled Thermodynamic and Two-phase Flow Model

NASA Astrophysics Data System (ADS)

Riel, N., Jr.; Bouilhol, P.; Van Hunen, J.; Velic, M.; Magni, V.

2016-12-01

Metamorphic and magmatic processes occurring in the deep crust ultimately control the chemical and physical characteristic of the continental crust. A complex interplay between magma intrusion, crystallization, and reaction with the pre-existing crust provide a wide range of differentiated magma and cumulates (and / or restites) that will feed the upper crustal levels with evolved melt while constructing the lower crust. With growing evidence from field and experimental studies, it becomes clearer that crystallization and melting processes are non-exclusive but should be considered together. Incoming H2O bearing mantle melts will start to fractionate to a certain extent, forming cumulates but also releasing heat and H2O to the intruded host-rock allowing it to melt in saturated conditions. The end-result of such dynamic system is a function of the amount and composition of melt input, and extent of reaction with the host which is itself dependent on the migration mode of the melts. To assess the dynamics of this deep magmatic system we developed a new 2-D two-phase flow code using finite volume method. Our formulation takes into account: (i) melt flow through a viscous porous matrix with temperature- and melt-content dependent host-rock viscosity, (ii) heat transfer, assuming local thermal equilibrium between solid and liquid, (iii) thermodynamic modelling of stable phases, (iv) injection of fractionated melt from crystallizing basalt at the Moho and (v) chemical advection of both the solid and liquid compositions. Here we present the core of our modelling approach, especially the petrological implementation. We show in details that our thermodynamic model can reproduce well both the sub- and supra solidus phase relationship and composition of the host-rock. We apply our method to an idealized amphibolite lower crust that is affected by a magmatic event represented by the intrusion of a wet mantle melt into the crust at Moho depth. The models [see Bouilhol et al. associated abstract for results] allow calculating the different proportion of phases present in the system through time.

Crystal structure and phase transformations of calcium yttrium orthophosphate, Ca 3Y(PO 4) 3

NASA Astrophysics Data System (ADS)

Fukuda, Koichiro; Iwata, Tomoyuki; Niwa, Takahiro

2006-11-01

Crystal structure and phase transformations of calcium yttrium orthophosphate Ca 3Y(PO 4) 3 were investigated by X-ray powder diffraction, selected-area electron diffraction, transmission electron microscopy and optical microscopy. The high-temperature phase is isostructural with eulytite, cubic (space group I4¯3d) with a=0.983320(5) nm, V=0.950790(8) nm 3, Z=4 and D x=3.45 Mg m -3. The crystal structure was refined with a split-atom model, in which the oxygen atoms are distributed over two partially occupied sites. Below the stable temperature range of eulytite, the crystal underwent a martensitic transformation, which is accompanied by the formation of platelike surface reliefs. The inverted crystal is triclinic (space group P1) with a=1.5726(1) nm, b=0.84267(9) nm, c=0.81244(8) nm, α=109.739(4)°, β=90.119(5)°, γ=89.908(7)°, V=1.0134(1) nm 3, Z=4 and D x=3.24 Mg m -3. The crystal grains were composed of pseudo-merohedral twins. The adjacent twin domains were related by the pseudo-symmetry mirror planes parallel to {101¯} with the composition surface {101¯}. When the eulytite was cooled relatively slowly from the stable temperature range, the decomposition reaction of Ca 3Y(PO 4) 3→ β-Ca 3(PO 4) 2+YPO 4 occurred.

Synthesis and Characterization of A2Mo3O 12 Materials

NASA Astrophysics Data System (ADS)

Young, Lindsay Kay

Negative thermal expansion (NTE) materials have attracted considerable research interest in recent decades. These unique materials shrink when heated, offering a potential means to control the overall thermal expansion of composites. Several families of materials display this behavior, the largest of which is the A2Mo3O12 family (also called the scandium tungstate family), in which A is a trivalent cation and M is molybdenum or tungsten. These materials show NTE in an orthorhombic structure, but many members transform to a monoclinic structure with positive expansion at low temperatures. Many properties of these materials are dependent on their elemental composition, especially the identity of the A3+ cation. This includes the magnitude of NTE, as well as the phase transition behavior as a function of temperature and pressure. It is also possible to create "mixed site" cation A2Mo3O12 materials, in which the A site is occupied by two different cations. These are described as AxA'2-xM3O12 materials, as the composition A:A' can vary. Creating these new compositions may result in different phase transition properties or the ability to tune the NTE properties of these materials. In this work, the focus was on synthesis and characterization of indium gallium molybdate (InxGa2-xM3O12). The non-hydrolytic sol-gel (NHSG) method was used to synthesize indium gallium molybdate while exploring a variety of reaction parameters. While the goal was to create stoichiometric, homogenous materials, it was found that this could not be accomplished using easily accessible parameters during NHSG reactions. However, it was discovered that certain conditions allowed unusually low temperature (230 °C) crystallization of these materials. Similar conditions were explored for single cation A2Mo3O12 materials, and it was determined that crystallization of indium molybdate, iron molybdate, and scandium molybdate was possible at temperatures of 230 or 300 °C. This extremely low temperature crystallization may provide the opportunity for exploring the in situ synthesis of polymer composites containing these materials, as the crystallization temperatures are compatible with many polymer systems. In the second part of this thesis, the high pressure behavior of a number of A2Mo3O12 and AA'Mo3O12 materials was studied. The open frameworks of NTE compounds are generally prone to pressure induced phase transitions. NTE materials may have to withstand high pressures during production or regular use of composites, thus understanding the high pressure behavior of these materials is necessary for effective application. Irreversible transitions to new phases or amorphization at high pressures could lead to failure of composites, as these phases are not expected to exhibit any NTE properties. Studies were carried out at the Advanced Photon Source at Argonne National Laboratory at pressures up to 5-7 GPa using a diamond anvil cell. The materials investigated could be divided into three groups based on distinct types of high pressure behavior. The room temperature monoclinic Group1 compounds (A2 = Al2, Fe2, FeAl, AlGa) underwent a similar sequence of reversible subtle phase transitions before undergoing a major structural transition to a common high pressure structure. The unit cell of this high pressure phase was successfully indexed, and the transition was found to be reversible upon decompression. Phase transition pressures increased with decreasing A-site cation radius. In contrast, Group2 materials (A = Cr, Y) retained their low temperature monoclinic structures up to the highest pressures investigated. The remaining materials (A2 = In2, InGa) underwent a different sequence of subtle transitions followed by an irreversible transition at higher pressures. The patterns belonging to these high pressure phases are unlike those of the first group. No patterns similar to InGaMo3O12 were found in the literature, while In2Mo3O12 may transform to the same high pressure polymorph as In2W3O12. The classification of A2Mo3O12 materials into several groups with distinct high pressure behavior adds pertinent knowledge to the field that may help elucidate the structures of previously studied materials, and ultimately may help predict the behavior of compositions that have not yet been explored.

Studies of Quaternary saline lakes-III. Mineral, chemical, and isotopic evidence of salt solution and crystallization processes in Owens Lake, California, 1969-1971

USGS Publications Warehouse

Smith, G.I.; Friedman, I.; McLaughlin, R.J.

1987-01-01

As a consequence of the 1969-1970 flooding of normally dry Owens Lake, a 2.4-m-deep lake formed and 20% of the 2-m-thick salt bed dissolved in it. Its desiccation began August 1969, and salts started crystallizing September 1970, ending August 1971. Mineralogic, brine-composition, and stable-isotope data plus field observations showed that while the evolving brine composition established the general crystallization timetable and range of primary and secondary mineral assemblages, it was the daily, monthly, and seasonal temperature changes that controlled the details of timing and mineralogy during this depositional process. Deuterium analyses of lake brine, interstitial brine, and hydrated saline phases helped confirm the sequence of mineral crystallizations and transformations, and they documented the sources and temperatures of waters involved in the reactions. Salts first crystallized as floating rafts on the lake surface. Natron and mirabilite, salts whose solubilities decrease greatly with lowering temperatures, crystallized late at night in winter, when surface-water temperatures reached their minima; trona, nahcolite, burkeite, and halite, salts with solubilities less sensitive to temperature, crystallized during the afternoon in summer, when surface salinities reached their maxima. However, different temperatures were generally associated with crystallization (at the surface) and accumulation (on the lake floor) because short-term temperature changes were transmitted to surface and bottom waters at different rates. Consequently, even when solubilities were exceeded at the surface, salts were preserved or not as a function of bottom-water temperatures. Halite, a nearly temperature-insensitive salt, was always preserved. Monitoring the lake-brine chemistry and mineralogy of the accumulating salts shows: (1) An estimated 0.9 ?? 106 tons of CO2 was released to the atmosphere or consumed by the lake's biomass prior to most salt crystallization. (2) After deposition, some salts reacted in situ to form other minerals in less than one month, and all salts (except halite) decomposed or recrystallized at least once in response to seasons. (3) Warming in early 1971 caused solution of all the mirabilite and some of the natron deposited a few months earlier, a deepening of the lake (though the lake-surface lowered), and an increase in dissolved solids. (4) Phase and solubility-index data suggest that at the close of desiccation, Na2CO3??7H2O, never reported as a mineral, could have been the next phase to crystallize. ?? 1987.

Structure and phase composition of welded joints modified by different welding techniques

NASA Astrophysics Data System (ADS)

Smirnov, Aleksander; Popova, Natalya; Nikonenko, Elena; Ozhiganov, Eugeniy; Ababkov, Nikolay; Koneva, Nina

2017-12-01

The paper presents the results of transmission electron microscopy (TEM) during the study of structure and phase composition of heat-affected zone (HAZ) of welded joints modified via four welding techniques, namely: electrode welding and electropercussive welding both with and without artificial flaws. The artificial flows represent aluminum pieces. TEM studies are carried out within the heat-affected zone, i.e. between the deposited and base metal, at 0.5 mm distance to the former. The 0.09C-2Mn-1Si-Fe steel type is used for welding. It is shown how the type of welding affects steel morphology, phase composition, defect structure and its parameters. The type of carbide phase is detected as well as the shape and location of particles. Volume fractions are estimated for the structural steel components, alongside with such parameters as the size of α-phase fragments, scalar and excess dislocation densities, and bending-torsion amplitude of the crystal lattice. Based on these results, we determine the welding technique and the structural component thus launching a mechanism of microcrack nucleation.

Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes

NASA Astrophysics Data System (ADS)

Baitinger, Michael; Böhme, Bodo; Ormeci, Alim; Grin, Yuri

Clathrates represent a family of inorganic materials called cage compounds. The key feature of their crystal structures is a three-dimensional (host) framework bearing large cavities (cages) with 20-28 vertices. These polyhedral cages bear—as a rule—guest species. Depending on the formal charge of the framework, clathrates are grouped in anionic, cationic and neutral. While the bonding in the framework is of (polar) covalent nature, the guest-host interaction can be ionic, covalent or even van-der Waals, depending on the chemical composition of the clathrates. The chemical composition and structural features of the cationic clathrates can be described by the enhanced Zintl concept, whereas the composition of the anionic clathrates deviates often from the Zintl counts, indicating additional atomic interactions in comparison with the ionic-covalent Zintl model. These interactions can be visualized and studied by applying modern quantum chemical approaches such as electron localizability.

Interactions between solidification and compositional convection in mushy layers

NASA Technical Reports Server (NTRS)

Worster, M. Grae

1994-01-01

Mushy layers are ubiquitous during the solidification of alloys. They are regions of mixed phase wherein solid crystals are bathed in the melt from which they grew. The matrix of crystals forms a porous medium through which the melt can flow, driven either by external forces or by its own buoyancy in a gravitational field. Buoyancy-driven convection of the melt depends both on temperature gradients, which are necessary for solidification, and on compositional gradients, which are generated as certain components of the alloy are preferentially incorporated in the solid phase and the remaining components are expelled into the melt. In fully liquid regions, the combined action of temperature and concentration on the density of the liquid can cause various forms of double-diffusive convection. However, in the interior of mushy regions the temperature and concentration are thermodynamically coupled so only single-diffusive convection can occur. Typically, the effect of composition on the buoyancy of the melt is much greater than the effect of temperature, and thus convection in mushy layers in driven primarily by the computational gradients within them. The rising interstitial liquid is relatively dilute, having come from colder regions of the mushy layer, where the liquidus concentration is lower, and can dissolve the crystal matrix through which it flows. This is the fundamental process by which chimneys are formed. It is a nonlinear process that requires the convective velocities to be sufficiently large, so fully fledged chimneys (narrow channels) might be avoided by means that weaken the flow. Better still would be to prevent convection altogether, since even weak convection will cause lateral, compositional inhomogeneities in castings. This report outlines three studies that examine the onset of convection within mushy layers.

Effect of silk sericin on morphology and structure of calcium carbonate crystal

NASA Astrophysics Data System (ADS)

Zhao, Rui-Bo; Han, Hua-Feng; Ding, Shao; Li, Ze-Hao; Kong, Xiang-Dong

2013-06-01

In this paper, silk sericin was employed to regulate the mineralization of calcium carbonate (CaCO3). CaCO3 composite particles were prepared by the precipitation reaction of sodium carbonate with calcium chloride solution in the presence of silk sericin. The as-prepared samples were collected at different reaction time to study the crystallization process of CaCO3 by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The results showed that silk sericin significantly affected the morphology and crystallographic polymorph of CaCO3. With increasing the reaction time, the crystal phase of CaCO3 transferred from calcite dominated to vaterite dominated mixtures, while the morphology of CaCO3 changed from disk-like calcite crystal to spherical vaterite crystal. These studies showed the potential of silk sericin used as a template molecule to control the growth of inorganic crystal.

The glass transition, crystallization and melting in Au-Pb-Sb alloys

NASA Technical Reports Server (NTRS)

Lee, M. C.; Allen, J. L.; Fecht, H. J.; Perepezko, J. H.; Ohsaka, K.

1988-01-01

The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO2-Al2O3-MgO Slags

NASA Astrophysics Data System (ADS)

Esfahani, Shaghayegh; Barati, Mansoor

2018-04-01

The crystallization kinetics of CaO-SiO2-Al2O3-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent ( n), rate coefficient ( K), and effective activation energy of crystallization ( E A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.

Phase transformations in SrAl2Si2O8 glass

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III; Bansal, Narottam P.

1992-01-01

Bulk glass of SrAl2Si2O8 composition crystallized at temperatures below 1000 C into hexacelsian, a hexagonal phase which undergoes a reversible, rapid transformation to an orthorhombic phase at 758 C, and at higher temperatures crystallized as celsian, a monoclinic phase. The glass transition temperature and crystallization onset temperature were determined to be 883 C and 1086 C, respectively, from DSC at a heating rate of 20 C/min. Thermal expansion of the various phases and density and bend strengths of cold isostatically pressed glass powder bars, sintered at various temperatures, were measured. The kinetics of the hexacelsian-to-celsian transformation for SrAl2Si2O8 were studied. Hexacelsian flakes were isothermally heat treated at temperatures from 1025-1200 C for various times. Avrami plots were determined by quantitatively measuring the amount of monoclinic celsian formed at various times using x ray diffraction. The Avrami constant was determined to be 1.1, suggesting a diffusionless, one dimensional transformation mechanism. The activation energy was determined from an Arrhenius plot of 1n k vs. 1/T to be 125 kilocal/mole. This value is consistent with a mechanism which transforms the layered hexacelsian structure to a three dimensional framework celsian structure and involves the breaking of Si-O bonds.

Emergent Low-Symmetry Phases and Large Property Enhancements in Ferroelectric KNbO 3 Bulk Crystals [Emergent Low-Symmetry Phases with Large Property Enhancement in Ferroelectric KNbO 3 Bulk Crystals

DOE PAGES

Lummen, Tom T. A.; Leung, J.; Kumar, Amit; ...

2017-06-19

The design of new or enhanced functionality in materials is traditionally viewed as requiring the discovery of new chemical compositions through synthesis. Large property enhancements may however also be hidden within already well-known materials, when their structural symmetry is deviated from equilibrium through a small local strain or field. Here, the discovery of enhanced material properties associated with a new metastable phase of monoclinic symmetry within bulk KNbO 3 is reported. This phase is found to coexist with the nominal orthorhombic phase at room temperature, and is both induced by and stabilized with local strains generated by a network ofmore » ferroelectric domain walls. While the local microstructural shear strain involved is only ≈0.017%, the concurrent symmetry reduction results in an optical second harmonic generation response that is over 550% higher at room temperature. Moreover, the meandering walls of the low-symmetry domains also exhibit enhanced electrical conductivity on the order of 1 S m -1. In conclusion, this discovery reveals a potential new route to local engineering of significant property enhancements and conductivity through symmetry lowering in ferroelectric crystals.« less

Phase transitions in mixed gas hydrates: experimental observations versus calculated data.

PubMed

Schicks, Judith M; Naumann, Rudolf; Erzinger, Jörg; Hester, Keith C; Koh, Carolyn A; Sloan, E Dendy

2006-06-15

This paper presents the phase behavior of multicomponent gas hydrate systems formed from primarily methane with small amounts of ethane and propane. Experimental conditions were typically in a pressure range between 1 and 6 MPa, and the temperature range was between 260 and 290 K. These multicomponent systems have been investigated using a variety of techniques including microscopic observations, Raman spectroscopy, and X-ray diffraction. These techniques, used in combination, allowed for measurement of the hydrate structure and composition, while observing the morphology of the hydrate crystals measured. The hydrate formed immediately below the three-phase line (V-L --> V-L-H) and contained crystals that were both light and dark in appearance. The light crystals, which visually were a single solid phase, showed a spectroscopic indication for the presence of occluded free gas in the hydrate. In contrast, the dark crystals were measured to be structure II (sII) without the presence of these occluded phases. Along with hydrate measurements near the decomposition line, an unexpected transformation process was visually observed at P-T-conditions in the stability field of the hydrates. Larger crystallites transformed into a foamy solid upon cooling over this transition line (between 5 and 10 K below the decomposition temperature). Below the transition line, a mixture of sI and sII was detected. This is the first time that these multicomponent systems have been investigated at these pressure and temperature conditions using both visual and spectroscopic techniques. These techniques enabled us to observe and measure the unexpected transformation process showing coexistence of different gas hydrate phases.

Phase study of SiO2-ZrO2 composites prepared from polymorphic combination of starting powders via a ball-milling followed by calcination

NASA Astrophysics Data System (ADS)

Musyarofah; Nurlaila, R.; Muwwaqor, N. F.; Saukani, M.; Kuswoyo, A.; Triwikantoro; Pratapa, S.

2017-04-01

The effects of SiO2-ZrO2 polymorphic combinations as starting powders and calcination temperature on phase composition of the SiO2-ZrO2 composites were studied. Stoichiometric (1:1 mol%) mixtures of the SiO2-ZrO2 composites were mechanically activated using a ball-milling for 5 h followed by calcinations at 1000, 1100 and 1200 °C for 3 h. The composites used in the present study were a-SiO2+ a-ZrO2, a-SiO2+ t-ZrO2, c-SiO2+ a-ZrO2 and c-SiO2+ t-ZrO2 which were symbolized by AA, AT, CA and CT, respectively. Prefixes a, t and c denote amorphous, tetragonal and cristobalite, respectively. The phase composition was determined by Rietveld analysis of X-ray diffraction (XRD) data using Rietica software. The identified phases for all calcined samples were a combination among t-ZrO2, c-SiO2, m-ZrO2 and zircon (ZrSiO4). Amorphous zirconia formed a transient tetragonal zirconia phase during heating, which reacted with silica to form zircon. The zircon phase was not found to form even at 1200 °C in the AT and CT mixtures and at 1100 °C in the CA mixture. The AA mixture in particular crystallized to form zircon at a lower temperature with more composition fraction than the others, ca 82.9 (14) mol%.

Formation mechanism of superconducting phase and its three-dimensional architecture in pseudo-single-crystal K xFe 2-ySe 2

DOE PAGES

Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.; ...

2016-02-11

Here, we report how the superconducting phase forms in pseudo-single-crystal K xFe 2-ySe 2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition.more » It should be emphasized that the phase separation in pseudo-single-crystal K xFe 2-ySe 2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.« less

Experimental investigation of condensation predictions for dust-enriched systems

NASA Astrophysics Data System (ADS)

Ustunisik, Gokce; Ebel, Denton S.; Walker, David; Boesenberg, Joseph S.

2014-10-01

Condensation models describe the equilibrium distribution of elements between coexisting phases (mineral solid solutions, silicate liquid, and vapor) in a closed chemical system, where the vapor phase is always present, using equations of state of the phases involved at a fixed total pressure (<1 bar) and temperature (T). The VAPORS code uses a CaO-MgO-Al2O3-SiO2 (CMAS) liquid model at T above the stability field of olivine, and the MELTS thermodynamics algorithm at lower T. Quenched high-T crystal + liquid assemblages are preserved in meteorites as Type B Ca-, Al-rich inclusions (CAIs), and olivine-rich ferromagnesian chondrules. Experimental tests of compositional regions within 100 K of the predicted T of olivine stability may clarify the nature of the phases present, the phase boundaries, and the partition of trace elements among these phases. Twenty-three Pt-loop equilibrium experiments in seven phase fields on twelve bulk compositions at specific T and dust enrichment factors tested the predicted stability fields of forsteritic olivine (Mg2SiO4), enstatite (MgSiO3), Cr-bearing spinel (MgAl2O4), perovskite (CaTiO3), melilite (Ca2Al2SiO7-Ca2Mg2Si2O7) and/or grossite (CaAl4O7) crystallizing from liquid. Experimental results for forsterite, enstatite, and grossite are in very good agreement with predictions, both in chemistry and phase abundances. On the other hand the stability of spinel with olivine, and stability of perovskite and gehlenite are quite different from predictions. Perovskite is absent in all experiments. Even at low oxygen fugacity (IW-3.4), the most TiO2-rich experiments do not crystallize Al-, Ti-bearing calcic pyroxene. The stability of spinel and olivine together is limited to a smaller phase field than is predicted. The melilite stability field is much larger than predicted, indicating a deficiency of current liquid or melilite activity models. In that respect, these experiments contribute to improving the data for calibrating thermodynamic models including MELTS.

Synthesis of Copper-Antimony-Sulfide Nanocrystals for Solution-Processed Solar Cells.

PubMed

Suehiro, Satoshi; Horita, Keisuke; Yuasa, Masayoshi; Tanaka, Tooru; Fujita, Katsuhiko; Ishiwata, Yoichi; Shimanoe, Kengo; Kida, Tetsuya

2015-08-17

The p-type nanocrystals (NCs) of copper-based chalcogenides, such as CuInSe2 and Cu2ZnSnS4, have attracted increasing attention in photovoltaic applications due to their potential to produce cheap solution-processed solar cells. Herein, we report the synthesis of copper-antimony-sulfide (CAS) NCs with different crystal phases including CuSbS2, Cu3SbS4, and Cu12Sb4S13. In addition, their morphology, crystal phase, and optical properties were characterized using transmission electron microscopy, X-ray diffractometry, UV-vis-near-IR spectroscopy, and photoemission yield spectroscopy. The morphology, crystal phase, and electronic structure were significantly dependent on the chemical composition in the CAS system. Devices were fabricated using particulate films consisting of CAS NCs prepared by spin coating without a high-temperature treatment. The CAS NC-based devices exhibited a diode-like current-voltage characteristic when coupled with an n-type CdS layer. In particular, the CuSbS2 NC devices exhibited photovoltaic responses under simulated sunlight, demonstrating its applicability for use in solution-processed solar cells.

Resistivity changes of some amorphous alloys undergoing nanocrystallization

NASA Astrophysics Data System (ADS)

Barandiarán, J. M.; Fernández Barquín, L.; Sal, J. C. Gómez; Gorría, P.; Hernando, A.

1993-10-01

The electrical resistivity of amorphous alloys with compositions: Fe 73.5Nb 3Cu 1Si 13.5B 9, Fe 86Zr 7Cu 1B 6 and Co 80Nb 8B 12 has been studied in the temperature range from 300 to 1100 K, where crystallization occurs. The products of crystallization and the grain size have been studied by X-ray diffraction. In a first step, all the alloys crystallize with small grains of a few nanometers in diameter (nanocrystalline state), and the resistivity behavior at this process accounts for the difference between the amorphous and nanocrystalline phases. The nanocrystalline phases are: α-Fe-Si, α-Fe and fcc Co for the three compounds studied respectively. A second process, at which grain growth and precipitation of intermetallic compounds and borides takes place, has been found for all the alloys. The resistivity is sensitive, not only to the total transformed sample amount, but to the topological distribution of the crystalline phases, and therefore shows a more complex behavior than other well established techniques, as differential scanning calorimetry. This supplementary information given by the resistivity is also discussed.

Thermal effect of diode-pumped solid state lasers based on composite crystals

NASA Astrophysics Data System (ADS)

Hao, Ming-ming; Lu, Guo-guang; Zhu, Hong-bo; Huang, Yun; En, Yun-fei

2013-12-01

Thermal effect of diode-pumped solid-state lasers (DPSSL) based on YAP/Tm:YAP composite crystal is studied by using of finite element method (FEM). It is found that the peak temperature in a composite rod decreases to less than 80% of that in a non-composite crystal. Thermal stress of composite rod is obviously reduced to less than 70% comparing with non-composite crystal. It is also demonstrated that length of thermal lens unchanged with increasing of un-doped crystal length, which means that beam quality of composite laser wouldn't be improved by non-composite crystal. Therefore, it is concluded that using composite crystal would benefit for the properties of temperature and heat stress while insignificance for beam quality of DPSSL.

Indications for a CO2-rich fluid cap in the uppermost part of the Laacher See Magma Chamber

NASA Astrophysics Data System (ADS)

Aßbichler, Donjá; Heuss-Aßbichler, Soraya; Kunzmann, Thomas

2017-04-01

Sanidinites are rare holocrystalline to hypocrystalline magmatic cumulates and are found as volcanic ejecta of potassic explosive volcanoes. They all have trachytic to phonolitic whole rock composition. Main constituent of these rocks is sanidine forming a framework of interlocking crystals creating miarolithic cavities. In this study we were investigating sodalite bearing sanidinites from the tephra deposits of the Laacher See Volcano, Eifel, Germany with the aim to decipher the processes in the uppermost, rigid part of the magma chamber. Macroscopically three different types can be distinguished: (1) dark haüyne-sanidinites, (2) bright haüyne-sanidinites and (3) nosean-sanidinites. Both types of haüyne-sanidinites contain glass, rich in vesicles, forming a film around most of the mineral grains or sometimes filling up the miarolithic cavities. Minor mineral phases are haüyne occurring within these cavities, mainly adjacent to plagioclase as well as clinopyroxene and biotite. Accessories are apatite, magnetite and titanite. In nosean-sanidinites glass is absent or occurs occasionally as a minor phase. Major crystals within the miarolithic cavities are nosean and calcite, while clinopyroxene and biotite are rarely observed. A special feature is the formation of HFSE minerals as euhedral crystals, including zircon, baddeleyite, pyrochlore and REE-apatites. The difference in mineral assemblage is also reflected in the whole rock composition of the investigated samples. Nosean-sanidinites are compared to haüyne-sanidinites (i) enriched in Na, Ca, Mn, S, Cl, Zr, U, Th, Hf, Zn and REE (+LOI) and (ii) depleted in K, Mg, Si, Ti, P, Ba, Sr and V. From dark haüyne-sanidinite over bright haüyne-sanidinite to nosean-sanidinites the mineral composition of the major phases shows following systematic trends: Ca content of sanidine decreases indicating decreasing temperature during crystallization. The minerals of the sodalite group show an increase of Na and CO2 whereas the content of Ca and SO4 decreases. Clinopyroxene observed in the haüyne-sanidinite has diospidic to hedenbergitic composition while in the nosean-sanidinites it is enriched in Mn (ferroan johannsenite with up to 0.55 apfu Mn; 15.5 wt.-% MnO). Several features indicate the presence of an aggressive fluid phase during formation of the nosean-sanidinites: all silicates expose etching structures such as jagged or rounded mineral surfaces, and/or holes and channels within the mineral grains. To a lesser extent these structures are also observed in the silicates of the bright haüyne-sanidinites. In nosean-sanidinites the etching holes are often filled by calcite. Occasionally these fillings are bounded by a calcite filled fluid vain. All these observations indicate the presence of a CO2-rich fluid phase. The sanidinites are suggested to be formed at late magmatic conditions from a phonolitic melt. The systematics in the textures indicates, that the minerals within the miarolithic cavities of the haüyne-sanidinites crystallized from an evolved, volatile rich phonolitic melt. In contrast the crystallization within the miarolithic pore space of the nosean-sanidinites took place in the rigid zone of the uppermost part of the magma chamber where the mineral forming processes are induced by CO2-rich fluid.

Effect of alkali ions (Na+, K+, Cs+) on reaction mechanism of CZTS nano-particles synthesis

NASA Astrophysics Data System (ADS)

Kumar, Suresh; Altosaar, Mare; Grossberg, Maarja; Mikli, Valdek

2018-04-01

The control of morphology, elemental composition and phase composition of Cu2ZnSnS4 (CZTS) nano-crystals depends on the control of complex formation and surface stabilization of nano-particles in solution-based synthesis in oleylamine. At temperatures ≥280 °C, the control of nano-crystal's morphology and homogenous growth is difficult because of fast poly-nuclear growth occurring at higher temperatures. In the present work the effect of oleylamine complex formation with different alkali ions (Na+, K+ and Cs+) on nano-crystals growth at synthesis temperature of 280 °C was studied. It was found that nano-powders synthesized in the presence of Na+ and K+ ions showed the formation of crystals of different sizes - small nano-particles (18 nm-30 nm), large aggregated crystals (few nm to 1 μm) and large single crystals (1 μm - 4 μm). The presence of Cs+ ions in the nano-powder synthesis in oleylamine-metal precursor-CsOH solution promoted growth of nano-crystals of homogenous size. It is proposed that the formed oleylamine-Cs complexes a) enhance the formation and stabilization of oleylamine-metal (Cu, Zn and Sn) complexes before the injection of sulphur precursor into the oleylamine-metal precursor solution and b) after addition of sulphur stabilize the fast nucleated nano-particles and promote diffusion limited growth.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Origin of mantle peridotite: Constraints from melting experiments to 16.5 GPa

NASA Astrophysics Data System (ADS)

Herzberg, Claude; Gasparik, Tibor; Sawamoto, Hiroshi

1990-09-01

Experimental data are reported for the melting of komatiite, peridotite, and chondrite compositions in the pressure range 5-16.5 GPa. All experiments were run using the multiple-anvil apparatus facilities at Nagoya and Stony Brook. Equilibrium between coexisting crystals and liquid is demonstrated to occur in less than 3 min in the 2100°C range. The anhydrous solidus in CaO-MgO-Al2O3-SiO2 has been calibrated and is shown to be about 100° higher than that for naturally occurring peridotite (KLB1). All melting curves have positive dT/dP. The effect of pressure is to expand the crystallization field of garnet at the expense of all other phases, resulting in a change in the liquidus phase from olivine to garnet at high pressures. The melting of rocks which contain the four crystalline phases olivine, orthopyroxene, clinopyroxene, and garnet is restricted to enstatite-rich compositions such as chondrite. For these it is demonstrated that melting is peritectic, rather than eutectic, and takes the form L+Opx = Ol+Cpx+Gt. Partial melting yields liquids with the following properties: 5 GPa for komatiite; and 10-15 GPa for liquid peridotite with about 40% MgO, but one that is unlike mantle peridotite in that it is distinctly enriched in silica. These results provide a test and refutation of the model that upper mantle peridotite originated by direct initial melting of a chondritic mantle (Herzberg and O'Hara, 1985). Unlike chondrite, partial melting of peridotite does not usually involve orthopyroxene. Instead, it occurs by the generation of ultrabasic liquids along a cotectic involving L+Ol+Cpx+Gt. Although the thermal and compositional characteristics of this cotectic have not been fully calibrated, it is very likely that it will degenerate into a thermal minimum (L+Ol+Cpx+Gt), compositionally similar to komatiite at 5 GPa and mantle peridotite at 10-15 GPa. Peridotite liquids that occupy a thermal minimum can be derived from those formed from the melting of chondrite by removal of orthopyroxene, followed by fractional crystallization of olivine, clinopyroxene, and garnet. The possibility exists that the thermal minimum is compositionally identical to mantle peridotite in the 10-15 GPa range. If this can be confirmed by experiment, the upper mantle can be understood as having originated by the fractional crystallization of peridotite liquids in a large-scale differentiation event, consistent with magma ocean models for an early Earth.

Effect of acidity on the citrate-nitrate combustion synthesis of alumina-zirconia composite powder

NASA Astrophysics Data System (ADS)

Chandradass, J.; Kim, Ki Hyeon

2009-12-01

Alumina-zirconia composite powders were produced by sol-gel autocombustion. 20 wt.% ZrO2-Al2O3 mixture precursor solutions were chelated by citric acid ions at different pH. DTA analysis shows sluggish decomposition at low pH, whereas there was rapid decomposition at high pH = 9. XRD patterns of the calcined powders showed that well crystallized powder with 100 % tetragonal phase and α-alumina phase is produced when pH = 0.58 (without ammonia addition). TEM characterization of composite powders revealed homogenous distribution of nanosized zirconia particles in the alumina matrix. FTIR analysis shows peaks at 590 cm-1 and 454 cm-1, which are identified as the characteristic absorption bands of Zr-O and Al-O.

Numerical modeling perspectives on zircon crystallization and magma reservoir growth at the Laguna del Maule volcanic field, central Chile

NASA Astrophysics Data System (ADS)

Andersen, N. L.; Dufek, J.; Singer, B. S.

2017-12-01

Magma reservoirs in the middle to upper crust are though to accumulate incrementally over 104 -105 years. Coupled crystallization ages and compositions of zircon are a potentially powerful tracer of reservoir growth and magma evolution. However, complex age distributions and disequilibrium trace element partitioning complicate the interpretation of the zircon record in terms of magmatic processes. In order to make quantitative predictions of the effects of magmatic processes that contribute reservoir growth and evolution—such as cooling and crystallization, magma recharge and mixing, and rejuvenation and remelting of cumulate-rich reservoir margins—we develop a model of zircon saturation and growth within a numerical framework of coupled thermal transfer, phase equilibrium, and magma dynamics. We apply this model to the Laguna del Maule volcanic field (LdM), located in central Chile. LdM has erupted at least 40 km3 of rhyolite from 36 vents distributed within a 250 km2 lake basin. Ongoing unrest demonstrates the large, silicic magma system beneath LdM remains active to this day. Zircon from rhyolite erupted between c. 23 and 1.8 ka produce a continuous distribution of 230Th-238U ages ranging from eruption to 40 ka, as well as less common crystal domains up to 165 ka and rare xenocrysts. Zircon trace element compositions fingerprint compositionally distinct reservoirs that grew within the larger magma system. Despite the dominantly continuous distributions of ages, many crystals are characterized by volumetrically substantial, trace element enriched domains consistent with rapid crystal growth. We utilize numerical simulations to assess the magmatic conditions required to catalyze these "blooms" of crystallization and the magma dynamics that contributed to the assembly of the LdM magma system.

Linking Plagioclase Zoning Patterns to Active Magma Processes

NASA Astrophysics Data System (ADS)

Izbekov, P. E.; Nicolaysen, K. P.; Neill, O. K.; Shcherbakov, V.; Plechov, P.; Eichelberger, J. C.

2015-12-01

Plagioclase, one of the most common and abundant mineral phases in volcanic products, will vary in composition in response to changes in temperature, pressure, composition of the ambient silicate melt, and melt H2O concentration. Changes in these parameters may cause dissolution or growth of plagioclase crystals, forming characteristic textural and compositional variations (zoning patterns), the complete core-to-rim sequence of which describes events experienced by an individual crystal from its nucleation to the last moments of its growth. Plagioclase crystals in a typical volcanic rock may look drastically dissimilar despite their spatial proximity and the fact that they have erupted together. Although they shared last moments of their growth during magma ascent and eruption, their prior experiences could be very different, as plagioclase crystals often come from different domains of the same magma system. Distinguishing similar zoning patterns, correlating them across the entire population of plagioclase crystals, and linking these patterns to specific perturbations in the magmatic system may provide additional perspective on the variety, extent, and timing of magma processes at active volcanic systems. Examples of magma processes, which may be distinguished based on plagioclase zoning patterns, include (1) cooling due to heat loss, (2) heating and/or pressure build up due to an input of new magmatic material, (3) pressure drop in response to magma system depressurization, and (4) crystal transfer between different magma domains/bodies. This review will include contrasting examples of zoning patters from recent eruptions of Karymsky, Bezymianny, and Tolbachik Volcanoes in Kamchatka, Augustine and Cleveland Volcanoes in Alaska, as well as from the drilling into an active magma body at Krafla, Iceland.

The Ackley City Batholith, southeastern Newfoundland: Evidence for crystal versus liquid-state fractionation

NASA Astrophysics Data System (ADS)

Whalen, J. B.

1983-08-01

The 345 ± 10 Ma old composite Ackley City Batholith of southeastern Newfoundland, consists largely of very felsic K-feldspar megacrystic granite and alaskite. Spatially related to the southeast contact of the alaskite are younger aplites and pegmatite, intrusive phases which are interpreted to be pan of a tilted, high level roof zone complex to the batholith. The compositions of the alaskite and roof zone complex define major and trace element gradients similar to those in voluminous high-silica eruptive suites; i.e., the alaskite is more chemically evolved (higher in Rb, lower in Ca, Fe, Mn, Ti, P, Sr, Ba and LREE) toward the roof. Apparently these chemical gradients in the batholith are restricted to the top 2 to 3 kms of the former magma chamber. Fractional crystallization is a plausible process for generating the chemical dispersion in the granites, although very high feldspar partition coefficients for Ba, Sr and Eu are required to generate the observed chemical gradients by a reasonable degree of fractional crystallization. Restriction of crystal fractionation to near the roof of the batholith may reflect a decreased viscosity which would facilitate crystal-liquid separation by processes such as filter pressing, flow differentiation or convective fractionation. The chemical gradients in these granites closely resemble those attributed in high-silica volcanics to the process of thermogravitational diffusion (TGD). Compositional gradients in the upper portion of a magma chamber are consistent with the TGD model. This model, although still poorly understood, is, like fractional crystallization, a plausible mechanism to generate the chemical features of the Ackley City granites.

Effect of zinc-borate glass addition on the thermal properties of the cordierite/Al2O3 composites containing nano-sized spinel crystal.

PubMed

Jo, Sinae; Kang, Seunggu

2013-11-01

Low-melting zinc-borate glass was added to the cordierite/Al2O3 composite in order to improve the sintering facility of Al2O3 and formation of nano-sized spinel crystal of high thermal conductivity. Increasing the ZnO/B2O3 ratio in the zinc-borate glass increased the ZnAl2O4 spinel and decreased the Al4B2O9 crystal peak intensities in X-ray diffraction pattern. The XRD peak intensities of the ZnAl2O4 spinel and Al4B2O9 crystals in the specimen containing 10 wt% zinc-borate glass (10G series) are higher than that of the specimen containing 5 wt% zinc-borate glass (5G series). The microstructures of most 10G series specimens had the flower-shaped crystal which was composed of 50 nm wide and 250 nm long needle-like crystals and identified as ZnAl2O4 spinel phase. The thermal conductivity of the 10G series specimen was higher than that of the 5G series in any ZnO/B2O3 ratio due to the formation of plenty of nano-sized ZnAl2O4 spinel of high thermal conductivity. Particularly, the thermal conductivity of the cordierite/Al2O3 composite containing 10 wt% zinc-borate glass of ZnO/B2O3 weight ratio = 1.5 was 3.8 W/Km which is much higher than that of the published value (3.0 W/Km).

Mass Spectrometric Investigation of Silicon Extremely Enriched in (28)Si: From (28)SiF4 (Gas Phase IRMS) to (28)Si Crystals (MC-ICP-MS).

PubMed

Pramann, Axel; Rienitz, Olaf

2016-06-07

A new generation of silicon crystals even further enriched in (28)Si (x((28)Si) > 0.999 98 mol/mol), recently produced by companies and institutes in Russia within the framework of a project initiated by PTB, were investigated with respect to their isotopic composition and molar mass M(Si). A modified isotope dilution mass spectrometric (IDMS) method treating the silicon as the matrix containing a so-called virtual element (VE) existing of the isotopes (29)Si and (30)Si solely and high resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) were applied in combination. This method succeeds also when examining the new materials holding merely trace amounts of (29)Si (x((29)Si) ≈ 5 × 10(-6) mol/mol) and (30)Si (x((30)Si) ≈ 7 × 10(-7) mol/mol) extremely difficult to detect with lowest uncertainty. However, there is a need for validating the enrichment in (28)Si already in the precursor material of the final crystals, silicon tetrafluoride (SiF4) gas prior to crystal production. For that purpose, the isotopic composition of selected SiF4 samples was determined using a multicollector magnetic sector field gas-phase isotope ratio mass spectrometer. Contaminations of SiF4 by natural silicon due to storing and during the isotope ratio mass spectrometry (IRMS) measurements were observed and quantified. The respective MC-ICP-MS measurements of the corresponding crystal samples show-in contrast-several advantages compared to gas phase IRMS. M(Si) of the new crystals were determined to some extent with uncertainties urel(M) < 1 × 10(-9). This study presents a clear dependence of the uncertainty urel(M(Si)) on the degree of enrichment in (28)Si. This leads to a reduction of urel(M(Si)) during the past decade by almost 3 orders of magnitude and thus further reduces the uncertainty of the Avogadro constant NA which is one of the preconditions for the redefinition of the SI unit kilogram.

Crystal structure, chemical composition, and extended defects of the high-Tc (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta compounds.

PubMed

Eibl, O

1995-02-15

This paper summarizes results obtained by high-resolution transmission electron microscopy on the crystal structure and microstructure of the (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta high-Tc superconducting oxides. The experimental basis for the work presented here are high-resolution structure images obtained at ultra-thin (3 nm) areas of carefully prepared transmission electron microscope (TEM) samples. The analysis was carried out on a 400 kV TEM equipped with a pole piece yielding 0.17 nm point-to-point resolution. From the images obtained the projected crystal potential of the cations can be extracted directly, as confirmed by detailed image simulation. Structural analysis of the oxygen sublattice remains an unsolved problem by high-resolution TEM (HRTEM), mainly because of the small scattering factors, and thus the contribution of the oxygen sublattice to the image contrast is small. The (BiPb)2Sr2Ca(n)-1CunO4 + 2n + delta phases are modulated structures that can be understood as an average structure plus a superimposed displacement field. The crystal structure consists of BiO double layers and perovskite-type cuboids (containing Sr, Ca, Cu, and O), which are sandwiched between the BiO double layers. The displacement field can be directly analyzed by HRTEM, and the largest displacement amplitudes of 70 pm were determined for the Bi atoms in the n = 1 compound. The chemical composition of the n = 2 and n = 3 compounds was determined by EDX in the TEM for the cation sublattice. A significant (Ca + Sr) deficiency (approximately 10%) with respect to Cu was found. The (Sr + Ca)/Cu mole fraction ratio was 1.31 for the Bi-2212 phase and 1.14 for the Bi(Pb)-2223 phase. The oxygen content cannot be determined by EDX in the TEM with the accuracy necessary for a correlation with electrical and superconducting properties. The defect structure present in these materials, that is, intergrown lamellae with different crystal structures and equal or different chemical compositions, stacking faults, and grain boundaries, is summarized. The importance of grain boundaries for understanding and improving superconducting properties is emphasized.

Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

PubMed

Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

2015-07-28

The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy.

Composition dependence of solid-phase epitaxy in silicon-germanium alloys: Experiment and theory

NASA Astrophysics Data System (ADS)

Haynes, T. E.; Antonell, M. J.; Lee, C. Archie; Jones, K. S.

1995-03-01

The rates of solid-phase epitaxy (SPE) in unstrained Si1-xGex alloys have been measured by time-resolved reflectivity for eight different alloy compositions, including both Si-rich and Ge-rich layers. Amorphous layers 300-400 nm thick were first formed in 8-μm-thick, relaxed, epitaxial Si1-xGex layers (0.02<=x<=0.87) by ion implantation of Si+. For each composition, the measured SPE rates spanned approximately two orders of magnitude. The alloy SPE rates are shown to be related to the regrowth rates of the two pure elements by a simple equation expressed in terms of the composition parameter x and having no adjustable parameters. The form of this equation implies that crystallization occurs by a serial attachment process at the amorphous-crystal interface and that the rate of attachment of each individual atom is determined by the identities of its four nearest neighbors. Such a process is consistent with the dangling-bond model proposed by Spaepen and Turnbull [in Laser-Solid Interactions and Laser Processing, edited by S. D. Ferris, H. J. Leamy, and J. M. Poate, AIP Conf. Proc. No. 50 (AIP, New York, 1979)] if the SPE rate is limited by the migration rate of dangling bonds rather than by their formation rate. Based on this analysis, an interpretation is proposed for the anomalously large activation energies that have been measured for SPE in some Si-rich compositions.

Growth of NBT-BT single crystals by flux method and their structural, morphological and electrical characterizations

NASA Astrophysics Data System (ADS)

Kanuru, Sreenadha Rao; Baskar, K.; Dhanasekaran, R.; Kumar, Binay

2016-05-01

In this paper, one of the important, eco-friendly polycrystalline material, (1-x)(Na0.5Bi0.5)TiO3 (NBT) - xBaTiO3 (BT) of different compositions (x=0.07, 0.06 and 0.05 wt%) around the morphotropic phase boundary (MPB) were synthesized by solid state reaction technique. And the single crystals with 13×7×7 mm3, 12×12×7 mm3 and 10×7×4 mm3 dimensions were grown by self flux method. The morphology, crystal structure and unit-cell parameters have been studied and the monoclinic phase has been identified for 0.07 wt% of BT. Higher BT concentration changes the crystal habit and the mechanism has been studied clearly. Raman spectroscopy at room-temperature confirms the presence of functional groups. The quality of the as grown single crystals was examined by high resolution x-ray diffraction analysis. The dielectric properties of the as grown crystals were investigated in the frequency range of 20 Hz-2 MHz from room temperature to 450 °C. The broad dielectric peak and frequency dispersion demonstrates the relaxor behavior of grown crystals. The dielectric constant (εr), transition temperature (Tm), and depolarization temperature (Td) of the grown crystals are found to be comparatively good. The diffusive factor (γ) from Curie-Weiss law confirms the as grown NBT-BT single crystals are relaxor in nature.

Effect of Partial Crystallization on the Structural and Luminescence Properties of Er3+-Doped Phosphate Glasses

PubMed Central

Lopez-Iscoa, Pablo; Salminen, Turkka; Hakkarainen, Teemu; Petit, Laeticia; Janner, Davide; Boetti, Nadia G.; Lastusaari, Mika; Pugliese, Diego; Paturi, Petriina; Milanese, Daniel

2017-01-01

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al2O3, TiO2, and ZnO was investigated. The morphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO3)2 crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er3+ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al2O3, TiO2, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er3+ ions are incorporated in the precipitated crystals only in this glass ceramic. PMID:28772833

Prediction of novel alloy phases of Al with Sc or Ta

PubMed Central

Bilić, Ante; Gale, Julian D.; Gibson, Mark A.; Wilson, Nick; McGregor, Kathie

2015-01-01

Using the evolutionary optimization algorithm, as implemented in the USPEX crystal predictor program, and first principles total energy calculations, the compositional phase diagrams for Al-Sc and Al-Ta alloy systems at zero temperature and pressure have been calculated. In addition to the known binary intermetallic phases, new potentially stable alloys, AlSc3 and AlTa7, have been identified in the Al-poor region of the phase diagram. The dynamic and thermal stability of their lattices has been confirmed from the calculated vibrational normal mode spectra in the harmonic approximation. PMID:25950915

Self-powered heat-resistant polymeric 1D nanowires and 3D micro/nanowire assemblies in a pressure-crystallized size-distributed graphene oxide/poly (vinylidene fluoride) composite

NASA Astrophysics Data System (ADS)

Tian, Pengfei; Lyu, Jun; Huang, Rui; Zhang, Chaoliang

2017-12-01

Piezoelectric one- (1D) and three-dimensional (3D) hybrid micro/nanostructured materials have received intense research interest because of their ability in capturing trace amounts of energy and transforming it into electrical energy. In this work, a size-distributed graphene oxide (GO) was utilized for the concurrent growth of both the 1D nanowires and 3D micro/nanowire architectures of poly (vinylidene fluoride) (PVDF) with piezoelectricity. The in situ formation of the polymeric micro/nanostructures, with crystalline beta phase, was achieved by the high-pressure crystallization of a well dispersed GO/PVDF composite, fabricated by an environmentally friendly physical approach. Particularly, by controlling the crystallization conditions of the binary composite at high pressure, the melting point of the polymeric micro/nanowires, which further constructed the 3D micro/nanoarchitectures, was nearly 30°C higher than that of the original PVDF. The large scale simultaneous formation of the 1D and 3D micro/nanostructures was attributed to a size-dependent catalysis of the GOs in the pressure-treated composite system. The as-fabricated heat-resistant hybrid micro/nanoarchitectures, consisting of GOs and piezoelectric PVDF micro/nanowires, may permit niche applications in self-powered micro/nanodevices for energy scavenging from their working environments.

Matrix- and tensor-based recommender systems for the discovery of currently unknown inorganic compounds

NASA Astrophysics Data System (ADS)

Seko, Atsuto; Hayashi, Hiroyuki; Kashima, Hisashi; Tanaka, Isao

2018-01-01

Chemically relevant compositions (CRCs) and atomic arrangements of inorganic compounds have been collected as inorganic crystal structure databases. Machine learning is a unique approach to search for currently unknown CRCs from vast candidates. Herein we propose matrix- and tensor-based recommender system approaches to predict currently unknown CRCs from database entries of CRCs. Firstly, the performance of the recommender system approaches to discover currently unknown CRCs is examined. A Tucker decomposition recommender system shows the best discovery rate of CRCs as the majority of the top 100 recommended ternary and quaternary compositions correspond to CRCs. Secondly, systematic density functional theory (DFT) calculations are performed to investigate the phase stability of the recommended compositions. The phase stability of the 27 compositions reveals that 23 currently unknown compounds are newly found to be stable. These results indicate that the recommender system has great potential to accelerate the discovery of new compounds.

Fabrication of nanocrystalline surface composite layer on Cu plate under ball collisions.

PubMed

Romankov, S; Park, Y C; Yoon, J M

2014-10-01

It was demonstrated that the severe plastic deformation of a surface induced by repeated ball collisions can be effectively used for fabrication of the nanocrystalline surface composite layers. The Cu disk was fixed at the top of a vibration chamber and ball treated. Al, Zr, Ni, Co and Fe were introduced into a Cu plate as contaminants from the grinding media one after the other by 15-min ball treatment. The composite structure was formed as a result of mechanical intermixing of the components. The particle size in as-fabricated layer ranged from 2 nm to 20 nm, with average values of about 7 nm. As-fabricated layer contained non-equilibrium multicomponent solid solution based on FCC Cu crystal structure, Zr-based phase, nanosized steel debris and amorphous phase. The hardness of the as-fabricated composite was almost ten times that of the initial Cu plate.

Synthesis and catalytic performance of ZSM-5/MCM-41 composite molecular sieve from palygorskite

NASA Astrophysics Data System (ADS)

Jiang, Jinlong; Wu, Mei; Yang, Yong; Duanmu, Chuansong; Chen, Jing; Gu, Xu

2017-10-01

ZSM-5/MCM-41 composite molecular sieve has been hydrothermally synthesized through a two-step crystallization process using palygorskite (PAL) as silicon and aluminum source. The products were characterized by various means and their catalytic properties for acetalization of cyclohexanone and esterification of acetic acid and n-butanol were also investigated. In the first step ZSM-5 zeolite could be formed from the acid-treated PAL after hydrothermal treatment using tetrapropylammonium bromide as template. XRD patterns, N2 adsorption and desorption data, and TEM images show that the composite obtained in the secondary step had a well-ordered mesoporous MCM-41 phase and a microporous ZSM-5 zeolite phase. Compared with ZSM-5, ZSM-5/MCM-41 composite possessed more total acid amount, weak acid sites and large pore structure due to the formation of MCM-41 and exhibited higher catalytic activity for the acetalization and esterification reaction.

Formation of a metastable hollandite phase from amorphous plagioclase: A possible origin of lingunite in shocked chondritic meteorites

NASA Astrophysics Data System (ADS)

Kubo, Tomoaki; Kono, Mari; Imamura, Masahiro; Kato, Takumi; Uehara, Seiichiro; Kondo, Tadashi; Higo, Yuji; Tange, Yoshinori; Kikegawa, Takumi

2017-11-01

We conducted high-pressure experiments in plagioclase with different anorthite contents at 18-27 GPa and 25-1750 °C using both a laser-heated diamond anvil cell and a Kawai-type multi-anvil apparatus to clarify the formation conditions of the hollandite phase in shocked chondritic and Martian meteorites. Lingunite (NaAlSi3O8-rich hollandite) was found first to crystallize from amorphous oligoclase as a metastable phase before decomposing into the final stable state. This process might account for the origin of lingunite found along with maskelynite in shocked chondritic meteorites. Metastable lingunite appeared at ∼20-24 GPa and ∼1100-1300 °C in laboratory tests lasting tens of minutes; however, it might also form at the higher temperatures and shorter time periods of shock events. In contrast, the hollandite phase was not observed during any stage of crystallization when using albite or labradorite as starting materials. The formation process of (Ca,Na)-hollandite in the labradorite composition found in Martian shergottites remains unresolved. The orthoclase contents of the hollandite phase both in shocked meteorites (2.4-8.2 mol%) and our oligoclase sample (3.9 mol%) are relatively high compared to the albite and labradorite samples (0.6 and 1.9 mol%, respectively). This might critically affect the crystallization kinetics of hollandite phase.

Hydrothermal synthesis of barium strontium titanate and bismuth titanate materials

NASA Astrophysics Data System (ADS)

Xu, Huiwen

Hydrothermal processing facilitates the synthesis of crystalline ceramic materials of varying composition or complex crystal structure. The present work can be divided into two parts. First is to study the low temperature hydrothermal synthesis of bismuth titanate. Second is to study both thermodynamic and kinetic aspects of the hydrothermally synthesized barium strontium titanate. A chelating agent was used to form a Bi-Ti gel precursor. By hydrothermally treating the Bi-Ti gel, crystalline bismuth titanate has been synthesized at 160°C for the first time. Microstructural evolution during the low temperature synthesis of bismuth titanate can be divided into two stages, including condensation of Bi-Ti gel particles and crystallization of bismuth titanate. Crystallization of bismuth titanate occurred by an in situ transformation mechanism at an early stage followed by a dissolution-reprecipitation mechanism. Phase separation was observed in hydrothermally synthesized barium strontium titanate (BST). By hydrothermally treating BST powders between 250°C--300°C, an asymmetrical miscibility gap was found in the BaTiO3-SrTiO 3 system at low temperatures (T ≤ 320°C). A subregular solid solution model was applied to calculate the equilibrium compositions and the Gibbs free energy of formation of BST solid solution at low temperatures (T ≤ 320°C). The Gibbs free energy of formation of Sr-rich BST phase is larger than that of Ba-rich BST phase. Kinetic studies of single phase BST solid solution at 80°C show that, compared to the BaTiO3 or Ba-rich BST, SrTiO3 and Sr-rich BST powders form at lower reaction rates.

High energy X-ray diffraction study of a dental ceramics–titanium functional gradient material prepared by field assisted sintering technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Witte, K., E-mail: kerstin.witte@uni-rostock.de; Bodnar, W.; Schell, N.

A functional gradient material with eleven layers composed of a dental ceramics and titanium was successfully consolidated using field assisted sintering technique in a two-step sintering process. High energy X-ray diffraction studies on the gradient were performed at High Energy Material Science beamline at Desy in Hamburg. Phase composition, crystal unit edges and lattice mismatch along the gradient were determined applying Rietveld refinement procedure. Phase analysis revealed that the main crystalline phase present in the gradient is α-Ti. Crystallinity increases stepwisely along the gradient with a decreasing increment between every next layer, following rather the weight fraction of titanium. Themore » crystal unit edge a of titanium remains approximately constant with a value of 2.9686(1) Å, while c is reduced with increasing amount of titanium. In the layer with pure titanium the crystal unit edge c is constant with a value of 4.7174(2) Å. The lattice mismatch leading to an internal stress was calculated over the whole gradient. It was found that the maximal internal stress in titanium embedded in the studied gradient is significantly smaller than its yield strength, which implies that the structure of titanium along the whole gradient is mechanically stable. - Highlights: • High energy XRD studies of dental ceramics–Ti gradient material consolidated by FAST. • Phase composition, crystallinity and lattice parameters are determined. • Crystallinity increases stepwisely along the gradient following weight fraction of Ti. • Lattice mismatch leading to internal stress is calculated over the whole gradient. • Internal stress in α-Ti embedded in the gradient is smaller than its yield strength.« less

Characterization of Ultra-high Temperature Ceramics via Transmission Electron Microscopy Relevant ZrB2-based Composites, TaC-based Composites and Oxides Containing SiC Chopped Fibers

DTIC Science & Technology

2015-03-06

was formed by ZrO2 rounded grains containing W traces and covered by H3BO3 acicular crystals deriving from hydration of B2O3 after exposure to...TaSi2 grains tended to form large pockets as wide as 3-8 m. Other spurious phases formed upon decomposition of the additive, were identified as SiC

Rare earth indates (RE: La-Yb): influence of the synthesis route and heat treatment on the crystal structure.

PubMed

Shukla, Rakesh; Grover, Vinita; Srinivasu, Kancharlapalli; Paul, Barnita; Roy, Anushree; Gupta, Ruma; Tyagi, Avesh Kumar

2018-05-15

Rare earth indates are an interesting class of compounds with rich crystallography. The present study explores the crystallographic phases observed in REInO3 (RE: La-Yb) systems and their dependence on synthesis routes and annealing temperature. All REInO3 compositions were synthesized by a solid state route as well as gel-combustion synthesis (GC) followed by annealing at different temperatures. The systems were well characterized by powder XRD studies and were analysed by Rietveld refinement for the structural parameters. The cell parameters were observed to decrease in accordance with the trend in ionic radii on proceeding from lighter to heavier rare earth ions. Interestingly, the synthesis route and the annealing temperature had a profound bearing on the phase relationships observed in the REInO3 series. The solid state synthesized samples depicted an orthorhombic phase (Pbnm) field for LaInO3 to SmInO3, followed by a hexagonal-type phase (P63cm) for GdInO3 to DyInO3. However, the phase field distribution was greatly influenced upon employing gel-combustion (GC) wherein both single-phasic hexagonal and orthorhombic phase fields were found to shrink. Annealing the GC-synthesized compositions to still higher temperatures (1250 °C) further evolved the phase boundaries. An important outcome of the study is observance of polymorphism in SmInO3 which crystallized in the hexagonal phase when synthesized by GC and orthorhombic phase by solid state synthesis. This reveals the all-important role played by synthesis conditions. The existence and energetics of the two polymorphs have been elucidated and discussed with the aid of theoretical studies.

Search for Al-26 effects in the Allende FUN inclusion C1. [Fractionation and Unknown Nuclear anomalies

NASA Technical Reports Server (NTRS)

Esat, T. M.; Lee, T.; Papanastassiou, D. A.; Wasserburg, G. J.

1978-01-01

The Mg isotopic composition of major and minor mineral phases in the Allende inclusion C1 is reported. The results are analyzed in order to establish whether the Mg isotopic composition is the same in different phases and whether Al-26 is present in a sample which exhibited fractionation and unknown nuclear (FUN) effects on other elements. It is found that a small Mg-26 excess exists in C1 and is correlated with the Al-27/Mg-24 ratio, indicating that Al-26 was present in C1 together with the more general nuclear anomalies. The results also reveal that isotopic homogeneity of Mg in Mg-rich phases in C1 is evident in both bulk samples and single microscopic crystals.

Large-scale magmatic layering in the Main Zone of the Bushveld Complex and episodic downward magma infiltration

NASA Astrophysics Data System (ADS)

Hayes, Ben; Ashwal, Lewis D.; Webb, Susan J.; Bybee, Grant M.

2017-03-01

The Bellevue drillcore intersects 3 km of Main and Upper Zone cumulates in the Northern Limb of the Bushveld Complex. Main Zone cumulates are predominately gabbronorites, with localized layers of pyroxenite and anorthosite. Some previous workers, using bulk rock major, trace and isotopic compositions, have suggested that the Main Zone crystallized predominantly from a single pulse of magma. However, density measurements throughout the Bellevue drillcore reveal intervals that show up-section increases in bulk rock density, which are difficult to explain by crystallization from a single batch of magma. Wavelet analysis of the density data suggests that these intervals occur on length-scales of 40 to 170 m, thus defining a scale of layering not previously described in the Bushveld Complex. Upward increases in density in the Main Zone correspond to upward increases in modal pyroxene, producing intervals that grade from a basal anorthosite (with 5% pyroxene) to gabbronorite (with 30-40% pyroxene). We examined the textures and mineral compositions of a 40 m thick interval showing upwardly increasing density to establish how this type of layering formed. Plagioclase generally forms euhedral laths, while orthopyroxene is interstitial in texture and commonly envelops finer-grained and embayed plagioclase grains. Minor interstitial clinopyroxene was the final phase to crystallize from the magma. Plagioclase compositions show negligible change up-section (average An62), with local reverse zoning at the rims of cumulus laths (average increase of 2 mol%). In contrast, interstitial orthopyroxene compositions become more primitive up-section, from Mg# 57 to Mg# 63. Clinopyroxene similarly shows an up-section increase in Mg#. Pyroxene compositions record the primary magmatic signature of the melt at the time of crystallization and are not an artefact of the trapped liquid shift effect. Combined, the textures and decoupled mineral compositions indicate that the upward density increase is produced by the downward infiltration of noritic magma into a previously emplaced plagioclase-rich crystal mush. Fresh noritic magma soaked down into the crystallizing anorthositic mush, partially dissolving plagioclase laths and assimilating Fe-enriched pore melt. The presence of multiple cycles showing upward increases in density in the Bellevue drillcore suggests that downward magma infiltration occurred episodically during crystallization of the Main Zone.

Segregation and Phase Transformations Along Superlattice Intrinsic Stacking Faults in Ni-Based Superalloys

NASA Astrophysics Data System (ADS)

Smith, T. M.; Esser, B. D.; Good, B.; Hooshmand, M. S.; Viswanathan, G. B.; Rae, C. M. F.; Ghazisaeidi, M.; McComb, D. W.; Mills, M. J.

2018-06-01

In this study, local chemical and structural changes along superlattice intrinsic stacking faults combine to represent an atomic-scale phase transformation. In order to elicit stacking fault shear, creep tests of two different single crystal Ni-based superalloys, ME501 and CMSX-4, were performed near 750 °C using stresses of 552 and 750 MPa, respectively. Through high-resolution scanning transmission electron microscopy (STEM) and state-of-the-art energy dispersive X-ray spectroscopy, ordered compositional changes were measured along SISFs in both alloys. For both instances, the elemental segregation and local crystal structure present along the SISFs are consistent with a nanoscale γ' to D019 phase transformation. Other notable observations are prominent γ-rich Cottrell atmospheres and new evidence of more complex reordering processes responsible for the formation of these faults. These findings are further supported using density functional theory calculations and high-angle annular dark-field (HAADF)-STEM image simulations.

Fragile morphotropic phase boundary and phase stability in the near-surface region of the relaxor ferroelectric (1 -x ) Pb (Z n1 /3N b2 /3) O3-x PbTi O3 : [001] field-cooled phase diagrams

NASA Astrophysics Data System (ADS)

Wang, Yaojin; Wang, Ding; Yuan, Guoliang; Ma, He; Xu, Feng; Li, Jiefang; Viehland, D.; Gehring, Peter M.

2016-11-01

We have examined the effects of field cooling on the phase diagram of the relaxor system (1 -x ) Pb (Z n1 /3N b2 /3) O3-x PbTi O3 (PZN-x PT ) for compositions near the morphotropic phase boundary (MPB). High-resolution diffraction measurements using Cu Kα x rays, which probe ≈3 μ m below the crystal surface, were made on field-cooled (FC) single-crystal specimens of PZN-4.5 %PT and PZN-6.5 %PT under electric fields of 1 and 2 kV/cm applied along [001] and combined with previous neutron diffraction data, which probe the entire crystal volume, for FC PZN-8 %PT [Ohwada et al., Phys. Rev. B 67, 094111 (2003), 10.1103/PhysRevB.67.094111]. A comparison to the zero-field-cooled (ZFC) PZN-x PT phase diagram reveals several interesting features: (1) The short-range monoclinic phase observed in the ZFC state on the low-PT side of the MPB is replaced by a monoclinic MA phase; (2) field cooling extends the tetragonal phase to higher temperatures and lower-PT concentrations; (3) the orthorhombic phase near the MPB is replaced by a monoclinic MC phase; (4) the vertical MPB in the ZFC phase diagram bends significantly towards the low-PT side in the FC state. These results demonstrate that both the phase stability and the nature of the MPB in PZN-PT within the near-surface regions are fragile in the presence of electric fields.

The effect of pigeon yolk sac fluid on the growth behavior of calcium carbonate crystals.

PubMed

Song, Juan; Cheng, Haixia; Shen, Xinyu; Tong, Hua

2015-03-01

Previous experiments have proved that thermodynamically unstable calcium carbonate vaterite can exist for long periods in the yolk sac of a pigeon embryo. The aim of this article was to demonstrate the effect of in vitro mineralization of yolk sac fluid on calcium carbonate by direct precipitation. Experiments were conducted using pigeon yolk sac fluid and using lecithin extracted from pigeon yolk sac fluid as a control to investigate the regulating effects of the organic components in the embryo on the formation of the calcium carbonate precipitate. Multiple characterization methods were employed to study the various morphological patterns, sizes, crystal growth, and crystal phase transformations of the calcium carbonate precipitates as regulated by the yolk sac fluid extracted at different stages of incubation. The experimental results demonstrate that as the incubation proceeds towards the later stages, the composition and environmental features of the yolk sac fluid become more favorable for the formation of relatively unstable calcium carbonate phases with high energies of the vaterite state. The experiments conducted with extracted lecithin as the template for crystal growth yielded similar results. A large amount of organic molecules with polar functional groups carried by the yolk sac fluid have strong effects and can both initially induce the crystallization and regulate the aggregation of calcium carbonate. Furthermore, this regulation process is found to be closely related to the lecithin contained in yolk sac fluid. These observations confirm the changes in yolk sac fluid composition during incubation have significant effects on the production of vaterite, which implicates the calcium transport during embryo growth. © 2015 Poultry Science Association Inc.

Band Structure Engineering by Substitutional Doping in Solid-State Solutions of [5-Me-PLY(O,O)]2B(1-x)Be(x) Radical Crystals.

PubMed

Bag, Pradip; Itkis, Mikhail E; Stekovic, Dejan; Pal, Sushanta K; Tham, Fook S; Haddon, Robert C

2015-08-12

We report the substitutional doping of solid-state spiro-bis(5-methyl-1,9-oxido-phenalenyl)boron radical ([2]2B) by co-crystallization of this radical with the corresponding spiro-bis(5-methyl-1,9-oxido-phenalenyl)beryllium compound ([2]2Be). The pure compounds crystallize in different space groups ([2]2B, P1̅, Z = 2; [2]2Be, P2₁/c, Z = 4) with distinct packing arrangements, yet we are able to isolate crystals of composition [2]2B(1-x)Be(x), where x = 0-0.59. The phase transition from the P1̅ to the P2₁/c space group occurs at x = 0.1, but the conductivities of the solid solutions are enhanced and the activation energies reduced for values of x = 0-0.25. The molecular packing is driven by the relative concentration of the spin-bearing ([2]2B) and spin-free ([2]2Be) molecules in the crystals, and the extended Hückel theory band structures show that the progressive incorporation of spin-free [2]2Be in the lattice of the [2]2B radical (overall bandwidth, W = 1.4 eV, in the pure compound) leads to very strong narrowing of the bandwidth, which reaches a minimum at [2]2Be (W = 0.3 eV). The results provide a graphic picture of the structural transformations undergone by the lattice, and at certain compositions we are able to identify distinct structures for the [2]2B and [2]2Be molecules in a single crystalline phase.

Influence of growth flux solvent on anneal-tuning of ground states in CaFe2As2

NASA Astrophysics Data System (ADS)

Roncaioli, Connor; Drye, Tyler; Saha, Shanta R.; Paglione, Johnpierre

2018-04-01

The effects of anneal-tuning of single-crystalline samples of CaFe2As2 synthesized via a molten Sn-flux method are investigated using x-ray diffraction, chemical composition, electrical transport, and magnetic susceptibility measurements in order to understand the role of growth conditions on the resultant phase diagram. Previous studies of CaFe2As2 crystals synthesized using a self-flux (FeAs) method revealed an ability to tune the structural and magnetic properties of this system by control of post-synthesis annealing conditions, resulting in an ambient pressure phase diagram that spans from tetragonal/orthorhombic antiferromagnetism to the collapsed tetragonal phase of this system. In this work, we compare previous results to those obtained on crystals synthesized via Sn flux, finding similar tunability in both self- and Sn-flux cases, but less sensitivity to annealing temperatures in the latter case, resulting in a temperature-shifted phase diagram.

High-Temperature Controlled Redox Crystallization Studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1985-01-01

The crystallization of silicates containing redox sensitive ions (e.g., Fe, Ti, Ce) must be performed under controlled and known redox conditions in order to obtain the maximum scientific benefit from experimental study. Furthermore, many compositions crystallize dense phases which settle during ground-based experiments. This settling influences the texture and chemical evolution of the crystallizing system. The purpose of this investigation is to develop a test system in which controlled redox experiments can be performed in the microgravity environment. The system will use solid ceramic oxygen electrolyte cells for control, measurements, and production of the required redox conditions. A preliminary design for a prototype is developed, the electrolyte and furnace tested, and a tentative protocol for experiment developed. The control parameter is to be established and a laboratory prototype built.

Phosphorus solubility in basaltic glass: Limitations for phosphorus immobilization in glass and glass-ceramics.

PubMed

Tarrago, M; Garcia-Valles, M; Martínez, S; Neuville, D R

2018-05-11

The composition of sewage sludge from urban wastewater treatment plants is simulated using P-doped basalts. Electron microscopy analyses show that the solubility of P in the basaltic melt is limited by the formation of a liquid-liquid immiscibility in the form of an aluminosilicate phase and a Ca-Mg-Fe-rich phosphate phase. The rheological behavior of these compositions is influenced by both phase separation and nanocrystallization. Upon a thermal treatment, the glasses will crystallize into a mixture of inosilicates and spinel-like phases at low P contents and into Ca-Mg-Fe phosphate at high P contents. Hardness measurements yield values between 5.41 and 7.66 GPa, inside the range of commercial glasses and glass-ceramics. Leaching affects mainly unstable Mg 2+ -PO 4 3- complexes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Kinetics of transformation of deformation processed gold-matrix composite

NASA Astrophysics Data System (ADS)

Wongpreedee, Kageeporn

Gold matrix Ḏeformation-processed M&barbelow;etal M&barbelow;etal C&barbelow;omposites (DMMC) have been developed that have better strength and conductivity than conventional gold alloys. However, DMMC possess metastable two-phase microstructures, and their strength and conductivity decrease after prolonged exposure to elevated temperatures. The kinetics of the transformation from the metastable two-phase microstructure to the equilibrium single-phase solid solution is of interest. This document describes a study of the elevated temperature stability of Au DMMC's and the relationship between microstructure and resistivity of three compositions: Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt. DMMC samples were prepared by a powder metallurgy technique and mechanical processes. The smallest final diameter of these wires was 120 mum. Avrami and Arrhenius relations were used to evaluate the kinetic transformation. The extensive deformation used to produce these composites reshaped the initially equi-axed powder particles into a nanofilamentary composite. Electrical resistivity measurements were used to determine the degree of transformation from the initial metastable nano-filamentary composite to the equilibrium solid solution condition. These measurements indicated that this transformation in Au-14 at%Ag, Au-7 at %Ag Au and Au-7 at %Pt DMMC wires proceeded with activation energies of 141, 156, and 167 kJ/mol, respectively. It is thought that these empirically determined activation energies differ from those determined in single crystal, planar interface Au-Ag and Au-Pt diffusion couples due to chemical potential, surface curvature, and strain effects. The DMMC systems reach the equilibrium solid solution condition faster than single crystal, planar interface systems for two reasons: (1) far more defects (dislocations, grain boundaries, vacancies from non-conservative dislocation motion, etc.) are present in the Au-Ag and Au-Pt DMMC composites, and (2) the small radius of curvature of the Ag and Pt filaments increases the chemical potential for diffusion in the DMMC.

Phonon scattering mechanisms dictating the thermal conductivity of lead zirconate titanate (PbZr 1- xTi xO 3) thin films across the compositional phase diagram

DOE PAGES

Foley, Brian M.; Paisley, Elizabeth A.; DiAntonio, Christopher; ...

2017-05-23

This paper represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr 1–xTi xO 3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropicmore » phase boundary (MPB, x = 0.48) where there is a 20%–25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ(x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. Finally, this is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).« less

Phonon scattering mechanisms dictating the thermal conductivity of lead zirconate titanate (PbZr 1- xTi xO 3) thin films across the compositional phase diagram

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foley, Brian M.; Paisley, Elizabeth A.; DiAntonio, Christopher

This paper represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr 1–xTi xO 3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropicmore » phase boundary (MPB, x = 0.48) where there is a 20%–25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ(x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. Finally, this is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).« less

Chemical Vapor Synthesis of Titanium Aluminides by Reaction of Aluminum Subchloride and Titanium Tetrachloride

NASA Astrophysics Data System (ADS)

Zakirov, Roman A.; Parfenov, Oleg G.; Solovyov, Leonid A.

2018-02-01

A new process for developing titanium aluminides (TiAls) using chemical vapor synthesis was investigated in a laboratory experiment. Aluminum subchloride (AlCl) was used as the reducing agent in the reaction with TiCl4 and the source of aluminum for Ti-Al alloy. Two types of products, with large crystals and fine particles, were fabricated. The large crystals were determined to be TiAl, with small amounts of Ti and Ti3Al phases. The composition of fine particles, on the other hand, varied in wide range.

Combining Pre- and Post-Nucleation Trajectories for the Synthesis of High FAU-Content Faujasite Nanocrystals from Organic-Free Sols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaleel, Maryam; Xu, Wenqian; Lesch, David A.

The effects of synthesis conditions on the FAU/EMT content and the size of nanocrystals, formed from inorganic aluminosilicate sols, were investigated. High resolution transmission electron microscopy imaging and comparison of experimental X-ray diffraction patterns with simulations demonstrated that all materials made starting from synthesis mixtures in the composition range (1.8-33) SiO2: 1 Al2O3: (2.7-33) Na2O: (41-1000) H2O contain FAU/EMT intergrowths. Compositions with low water content increase the FAU fraction up to 0.8 but the crystal size exceeds 100 nm. Extension of the higher FAU purity to nanocrystals was achieved only by first mixing the sol at high water content compositionsmore » that favor nanocrystal formation and then - after a certain time - lowering by freeze-drying the water to levels favoring the formation of FAU. Cryogenic transmission electron microscopy and small angle X-ray scattering from representative optically clear and colloidally stable precursor sols (aged and crystallized at ambient temperature) reveal the formation of amorphous aggregates before the detection of crystals, in agreement with earlier findings and an existing model for the aggregative growth of the zeolite MFI. The presence of these amorphous aggregates coincides with the aforementioned state of sol that preserves the original trajectory towards nano-crystals after the pronounced reduction of water content by freeze-drying. If water reduction by freeze-drying is applied earlier (before the detection of amorphous aggregates), the sol follows the low water content trajectory towards larger crystals. Despite this memory effect, the sol at this stage is still agnostic towards FAU or EMT formation, the relative content of which is dominantly determined by the final water content. These findings demonstrate that it is possible to combine the effects of pre-and post-nucleation sol composition to steer crystal size and crystal structure, respectively. They confirm precursor nanoparticle evolution, while they emphasize the importance of solution phase composition at both pre- and post-nucleation stages of aggregative crystal growth.« less

Superstructure and physical properties of skutterudite-related phase CoGe1.5Se1.5

NASA Astrophysics Data System (ADS)

Liang, Y.; Fang, B.; Zhu, X. M.; Liang, M. M.

2017-03-01

CoGe1.5Se1.5 skutterudite-related phase with a homogeneity range has been synthesized by solid-state reaction. The phase purity, homogeneity range, crystal structure, thermal stability and electrical resistivity were studied. XRD data indicates that CoGe1.5Se1.5 crystallized in a modification of the skutterudite CoAs3 type structure with space group R\\bar{3} (a = b = 11.751(1) Å, c = 14.36(1) Å). HRTEM-SAED shows more information about the superstructure to confirm the rhombohedral symmetry with space group R\\bar{3}. The lattice parameter of this skutterudite-related phase was found to be dependent on the concentration of Ge and Se. CoGe1.5Se1.5 decomposed between 1073 K and 1173 K under argon atmosphere investigated by in-situ XRD, suggesting a good thermal stability. CoGe1.49Se1.42, CoGe1.43Se1.34 and CoGe1.50Se1.15 dense bulk samples were obtained by hot-press technique. The chemical composition detected by FESEM/EDS suggests the homogeneity range and the existence of voids at framework positions. The electrical resistivity of the compounds decreases with increasing temperature, acting as a semiconductor. The chemical composition has a big influence on the value of electrical resistivity and energy gap.

Microstructure-property relationships in directionally solidified single crystal nickel-base superalloys

NASA Technical Reports Server (NTRS)

Mackay, R. A.; Nathal, M. V.

1986-01-01

Some of the microstructural features which influence the creep properties of directionally solidified and single crystal nickel-base superalloys are discussed. Gamma precipitate size and morphology, gamma-gamma lattice mismatch, phase instability, alloy composition, and processing variations are among the factors considered. Recent experimental results are reviewed and related to the operative deformation mechanisms and to the corresponding mechanical properties. Special emphasis is placed on the creep behavior of single crystal superalloys at high temperatures, where directional gamma coarsening is prominent, and at lower temperatures, where gamma coarsening rates are significantly reduced. It can be seen that very subtle changes in microstructural features can have profound effects on the subsequent properties of these materials.

Mechanochemical spinodal decomposition: a phenomenological theory of phase transformations in multi-component, crystalline solids

DOE PAGES

Rudraraju, Shiva; Van der Ven, Anton; Garikipati, Krishna

2016-06-10

Here, we present a phenomenological treatment of diffusion-driven martensitic phase transformations in multi-component crystalline solids that arise from non-convex free energies in mechanical and chemical variables. The treatment describes diffusional phase transformations that are accompanied by symmetry-breaking structural changes of the crystal unit cell and reveals the importance of a mechanochemical spinodal, defined as the region in strain-composition space, where the free-energy density function is non-convex. The approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. The governing equations describing mechanochemical spinodal decomposition aremore » variationally derived from a free-energy density function that accounts for interfacial energy via gradients of the rapidly varying strain and composition fields. A robust computational framework for treating the coupled, higher-order diffusion and nonlinear strain gradient elasticity problems is presented. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. An evaluation of available experimental phase diagrams and first-principles free energies suggests that mechanochemical spinodal decomposition should occur in metal hydrides such as ZrH 2-2c. The rich physics that ensues is explored in several numerical examples in two and three dimensions, and the relevance of the mechanism is discussed in the context of important electrode materials for Li-ion batteries and high-temperature ceramics.« less

Comparison of the properties of tonpilz transducers fabricated with 001 fiber-textured lead magnesium niobate-lead titanate ceramic and single crystals.

PubMed

Brosnan, Kristen H; Messing, Gary L; Markley, Douglas C; Meyer, Richard J

2009-11-01

Tonpilz transducers are fabricated from 001 fiber-textured 0.72Pb(Mg(1/3)Nb(2/3))O(3)-0.28PbTiO(3) (PMN-28PT) ceramics, obtained by the templated grain growth process, and PMN-28PT ceramic and Bridgman grown single crystals of the same composition. In-water characterization of single element transducers shows higher source levels, higher in-water coupling, and more usable bandwidth for the 81 vol % textured PMN-28PT device than for the ceramic PMN-28PT element. The 81 vol % textured PMN-28PT tonpilz element measured under large signals shows linearity in sound pressure levels up to 0.23 MV/m drive field but undergoes a phase transition due to a lowered transition temperature from the SrTiO(3) template particles. Although the textured ceramic performs well in this application, it could be further improved with compositional tailoring to raise the transition temperature and better processing to improve the texture quality. With these improvements textured piezoelectric ceramics will be viable options for medical ultrasound, actuators, and sonar applications because of their ease of processing, compositional homogeneity, and potentially lower cost than single crystal.

Composition-dependent stability of the medium-range order responsible for metallic glass formation

DOE PAGES

Zhang, Feng; Ji, Min; Fang, Xiao-Wei; ...

2014-09-18

The competition between the characteristic medium-range order corresponding to amorphous alloys and that in ordered crystalline phases is central to phase selection and morphology evolution under various processing conditions. We examine the stability of a model glass system, Cu–Zr, by comparing the energetics of various medium-range structural motifs over a wide range of compositions using first-principles calculations. Furthermore, we focus specifically on motifs that represent possible building blocks for competing glassy and crystalline phases, and we employ a genetic algorithm to efficiently identify the energetically favored decorations of each motif for specific compositions. These results show that a Bergman-type motifmore » with crystallization-resisting icosahedral symmetry is energetically most favorable in the composition range 0.63 < xCu < 0.68, and is the underlying motif for one of the three optimal glass-forming ranges observed experimentally for this binary system (Li et al., 2008). This work establishes an energy-based methodology to evaluate specific medium-range structural motifs which compete with stable crystalline nuclei in deeply undercooled liquids.« less

Demonstration of single crystal growth via solid-solid transformation of a glass

DOE PAGES

Savytskii, Dmytro; Knorr, Brian; Dierolf, Volkmar; ...

2016-03-18

Many advanced technologies have relied on the availability of single crystals of appropriate material such as silicon for microelectronics or superalloys for turbine blades. Similarly, many promising materials could unleash their full potential if they were available in a single crystal form. However, the current methods are unsuitable for growing single crystals of these oftentimes incongruently melting, unstable or metastable materials. Here we demonstrate a strategy to overcome this hurdle by avoiding the gaseous or liquid phase, and directly converting glass into a single crystal. Specifically, Sb 2S 3 single crystals are grown in Sb-S-I glasses as an example ofmore » this approach. In this first unambiguous demonstration of an all-solid-state glass → crystal transformation, extraneous nucleation is avoided relative to crystal growth via spatially localized laser heating and inclusion of a suitable glass former in the composition. Lastly, the ability to fabricate patterned single-crystal architecture on a glass surface is demonstrated, providing a new class of micro-structured substrate for low cost epitaxial growth, active planar devices, etc.« less

Fractional Crystallisation of Archaean Trondhjemite Magma at 12-7 Kbar: Constraints on Rheology of Archaean Continental Crust

NASA Astrophysics Data System (ADS)

Sarkar, Saheli; Saha, Lopamudra; Satyanarayan, Manavalan; Pati, Jayanta

2015-04-01

Fractional Crystallisation of Archaean Trondhjemite Magma at 12-7 Kbar: Constraints on Rheology of Archaean Continental Crust Sarkar, S.1, Saha, L.1, Satyanarayan, M2. and Pati, J.K.3 1. Department of Earth Sciences, Indian Institute of Technology Roorkee, Roorkee-247667, Haridwar, India, 2. HR-ICPMS Lab, Geochemistry Group, CSIR-National Geophysical Research Institute, Hyderabad-50007, India. 3. Department of Earth and Planetary Sciences, Nehru Science Centre, University of Allahabad, Allahabad-211002, India. Tonalite-Trondhjemite-Granodiorite (TTGs) group of rocks, that mostly constitute the Archaean continental crusts, evolved through a time period of ~3.8 Ga-2.7 Ga with major episodes of juvenile magma generations at ~3.6 Ga and ~2.7 Ga. Geochemical signatures, especially HREE depletions of most TTGs conform to formation of this type of magma by partial melting of amphibolites or eclogites at 15-20 kbar pressure. While TTGs (mostly sodic in compositions) dominates the Eoarchaean (~3.8-3.6 Ga) to Mesoarchaean (~3.2-3.0 Ga) domains, granitic rocks (with significantly high potassium contents) became more dominant in the Neoarchaean period. The most commonly accepted model proposed for the formation of the potassic granite in the Neoarchaean time is by partial melting of TTGs along subduction zones. However Archaean granite intrusive into the gabbro-ultramafic complex from Scourie, NW Scotland has been interpreted to have formed by fractional crystallization of hornblende and plagioclase from co-existing trondhjemitic gneiss. In this study we have studied fractional crystallization paths from a Mesoarchaean trondhjemite from the central Bundelkhand craton, India using MELTS algorithm. Fractional crystallization modeling has been performed at pressure ranges of 20 kbar to 7 kbar. Calculations have shown crystallization of garnet-clinopyroxene bearing assemblages with progressive cooling of the magma at 20 kbar. At pressure ranges 19-16 kbar, solid phases fractionating from the magma are mostly clinopyroxene with minor orthopyroxene. Plagioclase crystals appear at pressures ≤ 15 kbar. Plagioclase crystals are mostly albitic in composition (XAb ~0.70-0.75). At each pressure, with progressive cooling and fractionation of solid phases, crystal-melt ratio becomes significantly higher, magma becomes more depleted in Al2O3, MgO, with significant increase in K2O/Na2O ratio and water content. With progressive cooling and fractionation, overall composition of the magma changes from trondhjemitic to granitic, with increase in viscosity from 4.5 poise to 5.5 poise. The study thus reveals that fractional crystallization of trondhemitic magmas at different depths can form more potassic granitic magma with higher viscosity. As Hf isotope signatures from most Archaean TTGs reveal longer crustal residence, it is likely that granitic magmas that became more common in the Neoarchaean period, could also possibly been derived by fractional crystallization from trondhjemitic magmas in Mesoarchaean time. Granitic magmas hence generated have much higher viscosity compared to the parent trondhjemitic magma. Low viscosity of trondhjemitic magmas and low crystal-melt ratios in the initial stages of crystallization (as derived in this study), may be the cause of formation of large bodies of TTGs in Early Archaean period. Close to Neoarchaean period more granitic magmas are observed. In this study it has been observed that crystallization of these magmas lead to high crystal-melt ratios and the magmas have higher viscosity. Such change in composition from Early to Neoarchaean time must have made Archaean crusts stronger and hence more prone to deformation. This observation hence support occurrence of Phanerozoic style signatures from poly-deformed terrains of Neoarchaean time.

β-Ga2O3 versus ε-Ga2O3: Control of the crystal phase composition of gallium oxide thin film prepared by metal-organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Zhuo, Yi; Chen, Zimin; Tu, Wenbin; Ma, Xuejin; Pei, Yanli; Wang, Gang

2017-10-01

Gallium oxide thin films of β and ε phase were grown on c-plane sapphire using metal-organic chemical vapor deposition and the phase compositions were analyzed using X-ray diffraction. The epitaxial phase diagram was constructed as a function of the growth temperature and VI/III ratio. A low growth temperature and low VI/III ratio were beneficial for the formation of hexagonal-type ε-Ga2O3. Further structure analysis revealed that the epitaxial relationship between ε-Ga2O3 and c-plane sapphire is ε-Ga2O3 (0001) || Al2O3 (0001) and ε-Ga2O3 || Al2O3 . The structural evolution of the mixed-phase sample during film thickening was investigated. By reducing the growth rate, the film evolved from a mixed phase to the energetically favored ε phase. Based on these results, a Ga2O3 thin film with a phase-pure ε-Ga2O3 upper layer was successfully obtained.

Giant Magnetoelectric Energy Conversion Utilizing Inter-Ferroelectric Phase Transformations in Ferroics

NASA Astrophysics Data System (ADS)

Finkel, Peter; Staruch, Margo

Phase transition-based electromechanical transduction permits achieving a non-resonant broadband mechanical energy conversion see (Finkel et al Actuators, 5 [1] 2. (2015)) , the idea is based on generation high energy density per cycle , at least 100x of magnitude larger than linear piezoelectric type generators in stress biased [011]cut relaxor ferroelectric Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) single crystal can generate reversible strain >0.35% at remarkably low fields (0.1 MV/m) for tens of millions of cycles. Recently we demonstrated that large strain and polarization rotation can be generated for over 40 x 106cycles with little fatigue by realization of reversible ferroelectric-ferroelectric phase transition in [011] cut PIN-PMN-PT relaxor ferroelectric single crystal while sweeping through the transition with a low applied electric field <0.18 MV/m under mechanical stress. This methodology was extended in the present work to propose magnetoelectric (ME) composite hybrid system comprised of highly magnetostrictive alloymFe81.4Ga18.6 (Galfenol), and lead indium niobate-lead magnesium niobate-lead titanate (PIN-PMN-PT) domain engineered relaxor ferroelectric single crystal. A small time-varying magnetic field applied to this system causes the magnetostrictive element to expand, and the resulting stress forces the phase change in the relaxor ferroelectric single crystal. ME coupling coefficient was fond to achieve 80 V/cm Oe near the FR-FO phase transition that is at least 100X of magnitude higher than any currently reported values.

The special features of the crystal structure and properties of oxides with mixed conductivity based on lanthanum gallate

NASA Astrophysics Data System (ADS)

Politova, E. D.; Ivanov, S. A.; Kaleva, G. M.; Mosunov, A. V.; Rusakov, V. S.

2008-10-01

The paper presents a review of works on the synthesis, structural composition effects, phase transitions, and electrical conductivity properties of multicomponent solid solutions based on heterosubstituted lanthanum gallate (La,A)(Ga,M)O3 - y . High-temperature phase transitions and structural and charge ordering effects were studied. The presence of iron cations in different valence states was proved; the relative contents of these cations depended on the x parameter and nonstoichiometry parameter y of the base composition. For M = Fe, antiferromagnetic ordering was observed; its temperature interval was determined by the concentration of iron cations in the high-spin state. The total conductivity was found to increase as the concentration of transition metal cations grew because of an increase in the electronic conductivity component. The data on structural parameters and dc and ac conductivity substantiated the conclusion that the highest ionic conductivity and permeability to oxygen were characteristic of iron-containing oxides. The results obtained are evidence that crystal chemical factors play a determining role in the formation of the ion-conducting properties of anion-deficient perovskite-like oxides.

The directional crystallization of W-B-C- d-transition metal alloys

NASA Astrophysics Data System (ADS)

Paderno, Yuriy; Paderno, Varvara; Liashchenko, Alfred; Filipov, Volodymyr; Evdokimova, Alina; Martynenko, Anna

2006-09-01

Crystallization from the melt during arc melting and directional solidification during induction zone melting of pseudo-alloys tungsten carbide (WC)- MeB 2 ( Me—Ti, Zr, Cr) and a number of alloys of the W-B-C system (WB 0.12C 0.74; WB 0.25C 0.75; WB 0.34C 0.32; WB 0.49C 0.76; WB 0.59C 0.76; WB 0.89C 0.75; (WC) 0.9B 0.1) has been studied. It was shown that the alloys WC—80 mass%-ZrB 2—20 mass% and WC—72 mass%-WB—28 mass% are the closest ones to eutectic compositions. Investigation of the microstructure of eutectic alloys in the WC-WB system by thin foil method has revealed that both matrix and reinforcing phases are single crystalline. Hardness tests by indentation of the eutectic structure area ( P=10.3 N) do not result in radial crack formation, which is evidence of the essential plasticity of the obtained composite material. It is established that new ceramic-ceramic eutectic composite materials based on WC with transition metal diborides and with a boride phase of tungsten may be created. Such materials can be successfully applied in contemporary high-temperature techniques.

Steam-assisted crystallization of TPA{sup +}-exchanged MCM-41 type mesoporous materials with thick pore walls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hong Li; Zhang, Kun; Wang, Yi Meng, E-mail: ymwang@chem.ecnu.edu.cn

2012-07-15

Highlights: ► Mesoporous Ti-containing silica with thicker pore walls was synthesized. ► Ion-exchange and steam-assisted crystallization led to MCM-41/MFI composite. ► The introduction of Ti inhibited the formation of separated MFI particles. ► Lower temperature favored retaining mesoporous characteristics and morphology. -- Abstract: Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, {sup 1}H–{sup 13}C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show thatmore » the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.« less

Thermoelectric properties of Ge 1-xSn xTe crystals grown by vertical Bridgman method

NASA Astrophysics Data System (ADS)

Wu, C. C.; Ferng, N. J.; Gau, H. J.

2007-06-01

Single crystals of Ge 1-xSn xTe compounds with x=0, 0.8, 0.9 and 1.0 were grown by vertical Bridgman method. The crystalline phase and stochiometry for these crystals were investigated by X-ray diffraction, metallographic microscope as well as electron-probe microanalysis (EPMA). Electrical property of the as-grown samples was characterized using room temperature resistivity and Hall measurements. The thermoelectric behaviors for the Ge 1-xSn xTe crystals were studied by means of thermal and carrier transport measurements. Temperature dependences of resistivity, Seebeck coefficient and thermal conductivity for the various compositions of Ge 1-xSn xTe were analyzed. A two-valence band model was proposed to describe the temperature dependence of thermoelectric property of the Ge 1-xSn xTe crystals. The dimensionless thermoelectric figure of merit ZT for the alloys was evaluated and discussed.

Crystal nucleation in amorphous (Au/100-y/Cu/y/)77Si9Ge14 alloys

NASA Technical Reports Server (NTRS)

Thompson, C. V.; Greer, A. L.; Spaepen, F.

1983-01-01

Because, unlike most metallic glasses, melt-spun alloys of the series (Au/100-y/Cu/y/)77Si9Ge14 exhibit well separated glass transition and kinetic crystallization temperatures, crystallization can be studied in the fully relaxed amorphous phase. An isothermal calorimetric analysis of the devitrification kinetics of the amorphous alloy indicates sporadic nucleation and a constant growth rate. It is found for the cases of alloys with y values lower than 25 that the classical theory of homogeneous nucleation is consistent with observations, including transient effects. An analysis of the crystallization kinetics shows that slow crystal growth rates play an important role in glass formation in these alloys. Although the reduced glass transition temperature increases with Cu content, glass formation is more difficult at high Cu contents, perhaps because of a difference in nucleus composition.

Site occupancy, composition and magnetic structure dependencies of martensitic transformation in Mn2Ni1 + x Sn1-x.

PubMed

Kundu, Ashis; Ghosh, Subhradip

2017-11-29

A delicate balance between various factors such as site occupancy, composition and magnetic ordering seems to affect the stability of the martensitic phase in [Formula: see text] [Formula: see text] [Formula: see text]. Using first-principles DFT calculations, we explore the impacts of each one of these factors on the martensitic stability of this system. Our results on total energies, magnetic moments and electronic structures upon changes in the composition, the magnetic configurations and the site occupancies show that the occupancies at the 4d sites in the inverse Heusler crystal structure play the most crucial role. The presence of Mn at the 4d sites originally occupied by Sn and its interaction with the Mn atoms at other sites decide the stability of the martensitic phases. This explains the discrepancy between the experiments and earlier DFT calculations regarding phase stability in [Formula: see text]NiSn. Our results qualitatively explain the trends observed experimentally with regard to martensitic phase stability and the magnetisations in Ni-excess, Sn-deficient [Formula: see text]NiSn system.

Phase transformations and phase equilibria in the Co–Sn–Ti system in the crystallization interval

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fartushna, Iu.; Bulanova, M.; National Technical University of Ukraine, Kiev Polytechnical Institute, Kiev

2016-12-15

The Co–Sn–Ti system was studied in the crystallization interval (below ~50 at% Sn) by the methods of Scanning Electron Microscopy, microprobe analysis, Differential Thermal Analysis, X-ray diffraction. The liquidus and solidus projections and the melting diagram were constructed. Only Co{sub 2}TiSn(τ1) ternary compound (Heusler phase-L1{sub 2}) was found in equilibria with the liquid in the concentration interval studied. Taking into account our recent data, the liquidus projection is characterized by the fields of primary crystallization of (βTi), (Co), binary-based phases Ti{sub 3}Sn, Ti{sub 2}Sn, Ti{sub 5}Sn{sub 3}, Ti{sub 6}Sn{sub 5}, Ti{sub 2}Co, TiCo, TiCo{sub 2} (c), TiCo{sub 2} (h), TiCo{submore » 3}, βCo{sub 3}Sn{sub 2}, CoSn and ternary τ1. The solidus projection is characterized by thirteen three-phase fields, which result from invariant four-phase equilibria, five are of eutectic type (E) and eight of transition type (U) and the existence of one more region Ti{sub 2}Sn{sub 3}+βCoSn{sub 3}+(Sn) in the solidus projection is discussed. - Graphical abstract: Liquidus projection of the Ti–РЎРѕ –Sn system. Fields of crystallization, isotherms and monovariant lines. - Highlights: • The Ti–Co–Sn system is first studied in the composition range up to 50% of Sn. • Liquidus and solidus projections, melting diagram and reaction scheme are constructed. • One ternary compound form in the studied temperature interval: (Co{sub 2}TiSn(τ1)).« less

Effects of NO(y) aging on the dehydration dynamics of model sea spray aerosol.

PubMed

Woods, Ephraim; Heylman, Kevin D; Gibson, Amanda K; Ashwell, Adam P; Rossi, Sean R

2013-05-23

The reactions of NO(y) species in the atmosphere with sea spray aerosol replace halogen anions with nitrate. These experiments show the effect of increasing the nitrate content of model sea spray aerosol particles on the morphology changes and the phase transitions driven by changes in relative humidity (RH). The components of the model particles include H2O, Na+, Mg2+, Cl-, NO3-, and SO4(2-). Tandem differential mobility analyzer (TDMA) measurements yield the water content and efflorescence relative humidity (ERH) of these particles, and probe molecule spectroscopic measurements reveal subsequent phase transitions and partially characterize the salt composition on the surface of dry particles. The results show three effects of increasing the nitrate composition: decreasing the EFH (46 to 29%), production of a metastable aqueous layer on the surface of effloresced particles, and decreasing the sulfate content near the surface of dry particles. For the mixtures studied here, the initial crystallization event forms a core of NaCl. For particles that contain a substantial metastable aqueous layer following efflorescence, probe molecule spectroscopy shows a second crystallization at a lower RH. This subsequent phase transition is likely the formation of Na2SO4. Homogeneous nucleation theory (HNT) using a semiempirical formulation predicts the ERH of all mixtures within 2.0% RH, with a mean absolute deviation of 1.0%. The calculations suggest that structures associated with highly concentrated or supersaturated magnesium ions strongly affect the interfacial tension between the NaCl crystal nucleus and the droplet from which it forms.

A hybrid aluminium alloy and its zoo of interacting nano-precipitates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wenner, Sigurd, E-mail: sigurd.wenner@ntnu.no; Marioara, Calin Daniel; Andersen, Sigmund Jarle

An alloy with aluminium as its base element is heat treated to form a multitude of precipitate phases known from different classes of industrial alloys: Al–Cu(–Mg), Al–Mg–Si–Cu, and Al–Zn–Mg. Nanometer-sized needle-shaped particles define the starting point of the phase nucleation, after which there is a split in the precipitation sequence into six phases of highly diverse compositions and morphologies. There are several unique effects of phases from different alloy systems being present in the same host lattice, of which we concentrate on two: the replacement of Ag by Zn on the Ω interface and the formation of combined plates ofmore » the θ′ and C phases. Using atomically resolved scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy, we investigate the formation mechanisms, crystal structures and compositions of the precipitates. - Graphical abstract: Display Omitted - Highlights: • An aluminium alloy composition in-between the 2/6/7xxx systems was investigated. • Six different phases from the three systems coexist in an over-aged state. • All phases with 〈001〉{sub Al} coherencies can nucleate on 6xxx needle precipitates. • Modified theta′ and omega interfaces are observed.« less

Phase Change Characteristics of InxSb40-xTe60 Chalcogenide Alloy for Phase Change Random Access Memory

NASA Astrophysics Data System (ADS)

Yun, Jae-Jin; Lee, Won-Jong

2011-07-01

The InxSb40-xTe60 alloy was selected as a new alternative phase change material for Ge2Sb2Te5 (GST) for phase change random access memory (PRAM). The crystal structure of InxSb40-xTe60 was an α(Sb2Te3) rhombohedral (a=b=c, α=β=γ≠90°) single phase with identical lattice parameters in a wide composition range of In (0-28 at. %). The crystallization temperature and melting point of InxSb40-xTe60 were in the ranges of 149-219 °C and 608-614 °C, respectively, and similar to those of GST. The electric properties of InxSb40-xTe60 with a wide composition range of In contents showed the typical PRAM properties such as current-voltage (I-V), resistance-voltage (R-V), and switching behavior. The reset current of InxSb40-xTe60 decreased with increasing In content and the low power consumption and good retention can be realized by controlling In content. The ratio of the cell resistance and sheet resistance of amorphous InxSb40-xTe60 to those crystalline InxSb40-xTe60 were almost the same as or larger than those of GST. The cycling endurance test of InxSb40-xTe60 with a wide range of In contents showed the comparable results to GST. InxSb40-xTe60 was concluded to be a very promising phase change material for PRAM.

Online differentiation of mineral phase in aerosol particles by ion formation mechanism using a LAAP-TOF single-particle mass spectrometer

NASA Astrophysics Data System (ADS)

Marsden, Nicholas A.; Flynn, Michael J.; Allan, James D.; Coe, Hugh

2018-01-01

Mineralogy of silicate mineral dust has a strong influence on climate and ecosystems due to variation in physiochemical properties that result from differences in composition and crystal structure (mineral phase). Traditional offline methods of analysing mineral phase are labour intensive and the temporal resolution of the data is much longer than many atmospheric processes. Single-particle mass spectrometry (SPMS) is an established technique for the online size-resolved measurement of particle composition by laser desorption ionisation (LDI) followed by time-of-flight mass spectrometry (TOF-MS). Although non-quantitative, the technique is able to identify the presence of silicate minerals in airborne dust particles from markers of alkali metals and silicate molecular ions in the mass spectra. However, the differentiation of mineral phase in silicate particles by traditional mass spectral peak area measurements is not possible. This is because instrument function and matrix effects in the ionisation process result in variations in instrument response that are greater than the differences in composition between common mineral phases.In this study, we introduce a novel technique that enables the differentiation of mineral phase in silicate mineral particles by ion formation mechanism measured from subtle changes in ion arrival times at the TOF-MS detector. Using a combination of peak area and peak centroid measurements, we show that the arrangement of the interstitial alkali metals in the crystal structure, an important property in silicate mineralogy, influences the ion arrival times of elemental and molecular ion species in the negative ion mass spectra. A classification scheme is presented that allowed for the differentiation of illite-smectite, kaolinite and feldspar minerals on a single-particle basis. Online analysis of mineral dust aerosol generated from clay mineral standards produced mineral fractions that are in agreement with bulk measurements reported by traditional XRD (X-ray diffraction) analysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Yogesh; Yadav, K. L., E-mail: klyadav35@yahoo.com

The magnetoelectric composites of inverse spinel ferrite CoMn{sub 0.2}Fe{sub 1.8}O{sub 4} (CMFO) and Bi{sub 0.5}Na{sub 0.5}TiO{sub 3} (BNT) with general formula (x) Bi{sub 0.5}Na{sub 0.5}TiO{sub 3} – (1-x) CoMn{sub 0.2}Fe{sub 1.8}O{sub 4} have been prepared through hybrid processing route. X-ray diffraction pattern reveal that CFMO crystallizes in inverse cubic spinel phase and BNT in rhombohedral perovskite phase. Dielectric constant and dielectric loss were reported with frequency at room temperature. The magnetic properties of the composites were calculated from the Magnetization – Magnetic field (M-H) hysteresis loops obtained at room temperature. Ferroelectric properties of the composites were also investigated using Polarizationmore » –Electric field (P-E) hysteresis loops.« less

Nanostructured crystals of fluorite phases Sr{sub 1−x}R{sub x}F{sub 2+x} (R Are Rare Earth Elements) and their ordering: 10. Ordering under spontaneous crystallization and annealing of Sr{sub 1−x}R{sub x}F{sub 2+x} Alloys (R = Tb-Lu, Y) with 23.8–36.1 mol % RF{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sulyanova, E. A., E-mail: sulyanova@gmail.com; Karimov, D. N.; Sulyanov, S. N.

The products of spontaneous crystallization (at a cooling rate of ∼200 K/min) of Sr{sub 1−x}R{sub x}F{sub 2+x} melts in the homogeneity range of the fluorite phase have been investigated. Thirty-two irrational compositions with 23.8–36.1 mol % RF{sub 3} and eight rational Sr{sub 2}RF{sub 7} compositions are obtained. With respect to the RF{sub 3} content, these compositions form five groups: (1) Sr{sub 0.762}R{sub 0.238}F{sub 2.238} (23.8% RF{sub 3}), (2) Sr{sub 0.744}R{sub 0.256}F{sub 2.256} (25.6%), (3) Sr{sub 0.718}R{sub 0.282}F{sub 2.282} (28.2%), (4) Sr{sub 2}RF{sub 7} (33.3%), and (5) Sr{sub 0.639}R{sub 0.361}F{sub 2.361} (36.1%). R = Tb-Lu, Y for all groups. Quenching meltsmore » of group 5 with R = Tb, Dy, and Ho leads to the formation of ordered phases with the trigonal distortion of the rhβ-Na{sub 7}Zr{sub 6}F{sub 31} type, while for melts of group 5 with R = Lu, quenching yields a phase of the trigonal rhα′-Sr{sub 4}Lu{sub 3}F{sub 17} type. In group 5 with R = Y, Er, Tm, or Yb and in groups 1–4 with all REEs, fluorite phases are formed. Annealing at 900 ± 20°C for 96 h with subsequent cooling at a rate of ∼200 K/min expands the variety of ordered phases: a phase with a new r type of orthorhombic distortion is formed in group 1 with R = Lu, in group 2 with R = Tm or Lu, and in group 3 with R = Ho-Lu, Y; a t-Sr{sub 2}RF{sub 7} phase with tetragonal distortion is formed in group 4 with R = Tb-Er, Y; and a phase of trigonal rhα′ type is formed in group 5 with R = Y, Yb, or Lu. A fluorite phase arises in group 1 with R = Tb-Lu, Y as a result of quenching and annealing. The tendency to ordering becomes more pronounced with an increase in the RF{sub 3} content and REE atomic number. The annealing conditions do not provide equilibrium or the completely ordered state of all alloys.« less

Meretrix lusoria--a natural biocomposite material: in situ analysis of hierarchical fabrication and micro-hardness.

PubMed

Zhu, Zhihong; Tong, Hua; Ren, Yaoyao; Hu, Jiming

2006-01-01

The ultrastructure of clam (Meretrix lusoria) was investigated by means of scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction analyzer (XRD) combining with in situ texture decalcified technique and the micro-hardness of clam was determined, in order to understand the spatial relationship between the mineral phase and organic matrix and further explain the correlation between the property and structure. The results showed that hierarchical fabrication is the major structure character of this mollusc shell. There is specific braided structure forming from domains composed of needle-like structure made up of the single crystal of aragonite. High magnification TEM image of clam indicates the intracrystal region of the aragonite single crystal is made up of subgrain phase and some amorphous substance. There are various crystal grain growth preferential orientations in the different growth direction of the shell. An amount of organic microtubule distribute evenly in the base of calcium carbonate as reinforcement phase. The mechanical property of this natural biological composite is better than other aragonite layer of mollusc shells and pearls according to the data of micro-hardness testing. The braided structure and organic microtubule reinforcement phase are responsible for its high mechanical performance. The stereo hierarchical fabrication of clam was elucidated for the first time.

Fluorine-ion conductivity of different technological forms of solid electrolytes R{sub 1–y}M{sub y}F{sub 3–y} (LaF{sub 3} Type ) (M = Ca, Sr, Ba; R Are Rare Earth Elements)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sorokin, N. I., E-mail: nsorokin1@yandex.ru; Sobolev, B. P.

We have investigated the conductivity of some representatives of different technological forms of fluoride-conducting solid electrolytes R{sub 1–y}M{sub y}F{sub 3–y} (M = Ca, Sr, Ba; R are rare earth elements) with an LaF{sub 3} structure: single crystals, cold- and hot-pressing ceramics based on a charge prepared in different ways (mechanochemical synthesis, solid-phase synthesis, and fragmentation of single crystals), polycrystalline alloys, etc. It is shown (by impedance spectroscopy), that different technological forms of identical chemical composition (R, M, y) exhibit different electrical characteristics. The maximum conductivity is observed for the single-crystal form of R{sub 1–y}M{sub y}F{sub 3–y} tysonite phases, which providesmore » (in contrast to other technological forms) the formation of true volume ion-conducting characteristics.« less

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

High-throughput search of ternary chalcogenides for p-type transparent electrodes

PubMed Central

Shi, Jingming; Cerqueira, Tiago F. T.; Cui, Wenwen; Nogueira, Fernando; Botti, Silvana; Marques, Miguel A. L.

2017-01-01

Delafossite crystals are fascinating ternary oxides that have demonstrated transparent conductivity and ambipolar doping. Here we use a high-throughput approach based on density functional theory to find delafossite and related layered phases of composition ABX2, where A and B are elements of the periodic table, and X is a chalcogen (O, S, Se, and Te). From the 15 624 compounds studied in the trigonal delafossite prototype structure, 285 are within 50 meV/atom from the convex hull of stability. These compounds are further investigated using global structural prediction methods to obtain their lowest-energy crystal structure. We find 79 systems not present in the materials project database that are thermodynamically stable and crystallize in the delafossite or in closely related structures. These novel phases are then characterized by calculating their band gaps and hole effective masses. This characterization unveils a large diversity of properties, ranging from normal metals, magnetic metals, and some candidate compounds for p-type transparent electrodes. PMID:28266587

Modeling of nanostructured porous thermoelastic composites with surface effects

NASA Astrophysics Data System (ADS)

Nasedkin, A. V.; Nasedkina, A. A.; Kornievsky, A. S.

2017-01-01

The paper presents an integrated approach for determination of effective properties of anisotropic porous thermoelastic materials with a nanoscale stochastic porosity structure. This approach includes the effective moduli method for composite me-chanics, the simulation of representative volumes and the finite element method. In order to take into account nanoscale sizes of pores, the Gurtin-Murdoch model of surface stresses and the highly conducting interface model are used at the borders between material and pores. The general methodology for determination of effective properties of porous composites is demonstrated for a two-phase composite with special conditions for stresses and heat flux discontinuities at the phase interfaces. The mathematical statements of boundary value problems and the resulting formulas to determine the complete set of effective constants of the two-phase composites with arbitrary anisotropy and with surface properties are described; the generalized statements are formulated and the finite element approximations are given. It is shown that the homogenization procedures for porous composites with surface effects can be considered as special cases of the corresponding procedures for the two-phase composites with interphase stresses and heat fluxes if the moduli of nanoinclusions are negligibly small. These approaches have been implemented in the finite element package ANSYS for a model of porous material with cubic crystal system for various values of surface moduli, porosity and number of pores. It has been noted that the magnitude of the area of the interphase boundaries has influence on the effective moduli of the porous materials with nanosized structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, J. P.; Wang, Y. D.; Hao, Y. L.

Two main explanations exist for the deformation mechanisms in Ti-Nb-based gum metals, i.e. the formation of reversible nanodisturbance and reversible stress-induced martensitic transformation. In this work, we used the in situ synchrotron-based high-energy X-ray diffuse-scattering technique to reveal the existence of a specific deformation mechanism, i.e. deformation-induced spatially confined martensitic transformations, in Ti-24Nb-4Zr-8Sn-0.10O single crystals with cubic 13 parent phase, which explains well some anomalous mechanical properties of the alloy such as low elastic modulus and nonlinear superelasticity. Two kinds of nanosized martensites with different crystal structures were found during uniaxial tensile loading along the [11 0](beta) axis at roommore » temperature and 190 K, respectively. The detailed changes in the martensitic phase transformation characteristics and the transformation kinetics were experimentally observed at different temperatures. The domain switch from non-modulated martensite to a modulated one occurred at 190 K, with its physical origin attributed to the heterogeneity of local phonon softening depending on temperature and inhomogeneous composition in the parent phase. An in-depth understanding of the formation of stress-induced spatially confined nanosized martensites with a large gradient in chemical composition may benefit designs of high-strength and high-ductility alloys. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.« less

Preparation and crystalline studies of PVDF hybrid composites

NASA Astrophysics Data System (ADS)

Chethan P., B.; Renukappa, N. M.; Sanjeev, Ganesh

2018-04-01

The conducting polymer composites have become increasingly important for electrical and electronic applications due to their flexibility, easy of processing, high strength and low cost. A flexible conducting polymer hybrid composite was prepared by melt mixing of nickel coated multi-walled carbon nanotubes (Ni-MWNT) and graphitized carbon nanofibres (GCNF) in Polyvinylidene fluoride (PVDF) matrix. The crystalline structures of the nano composites were studied by X-ray diffraction (XRD) method and showed characteristic peaks at 17.7°, 18.5°, 20° and 26.7° of 2θ. The β phase crystalline nature of the composite films, degree of crystallinity, melting temperature and crystallization behavior of the hybrid composites were studied using appropriate characterization techniques. The filler in the insulating polymer matrix plays crucial role to improve the crystallinity of the composites.

Effect of Homogenizing Heat Treatment of Liquid Aluminum-Copper Alloys on the Structure of Rapidly Crystallized Specimens

NASA Astrophysics Data System (ADS)

Astaf'ev, V. V.; Kurochkin, A. R.; Yablonskikh, T. I.; Brodova, I. G.; Popel', P. S.

2017-11-01

Centrifugal casting into a massive slot chill mold was used to prepare two series of specimens of alloys of the Al - Cu system, containing from 10 to 32.2 at.% Cu. The first series was fabricated without a homogenizing heat treatment of the melt, while the second series was fabricated with heating of the melt to 1400°C. Both kinds of specimens were cast at the same temperature in order to provide for the same cooling rate of about 104 K/sec. The structures, phase compositions and microhardnesses of the structural components are compared. It is established that the homogenizing heat treatment changes the kinetics of crystallization and, hence, the proportion of phases in the alloy structure and the copper content in them.

Linking Plagioclase Zoning Patterns to Active Magma Processes

NASA Astrophysics Data System (ADS)

Izbekov, P. E.; Nicolaysen, K. P.; Neill, O. K.; Shcherbakov, V.; Eichelberger, J. C.; Plechov, P.

2016-12-01

Plagioclase, one of the most common and abundant mineral phases in volcanic products, will vary in composition in response to changes in temperature, pressure, composition of the ambient silicate melt, and melt H2O concentration. Changes in these parameters may cause dissolution or growth of plagioclase crystals, forming characteristic textural and compositional variations (zoning patterns), the complete core-to-rim sequence of which describes events experienced by an individual crystal from its nucleation to the last moments of its growth. Plagioclase crystals in a typical volcanic rock may look drastically dissimilar despite their spatial proximity and the fact that they have erupted together. Although they shared last moments of their growth during magma ascent and eruption, their prior experiences could be very different, as plagioclase crystals often come from different domains of the same magma system. Distinguishing similar zoning patterns, correlating them across the entire population of plagioclase crystals, and linking these patterns to specific perturbations in the magmatic system may provide additional perspective on the variety, extent, and timing of magma processes at active volcanic systems. Examples of magma processes, which may be distinguished based on plagioclase zoning patterns, include (1) cooling due to heat loss, (2) heating and/or pressure build up due to an input of new magmatic material, (3) pressure drop in response to magma system depressurization, and (4) crystal transfer between different magma domains/bodies. This review will include contrasting examples of zoning patters from recent eruptions of Augustine and Cleveland Volcanoes in Alaska, Sakurajima Volcano in Japan, Karymsky, Bezymianny, and Tolbachik Volcanoes in Kamchatka, as well as from the drilling into an active magma body at Krafla, Iceland.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parab, Niranjan D.; Roberts, Zane A.; Harr, Michael H.

Fracture of crystals and subsequent frictional heating are associated with formation of hot spots in energetic composites such as polymer bonded explosives (PBXs). Traditional high speed optical imaging methods cannot be used to study the dynamic sub-surface deformation and fracture behavior of such materials due to their opaque nature. In this study, high speed synchrotron X-ray experiments are conducted to visualize the in situ deformation and fracture mechanisms in PBXs manufactured using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and hydroxyl-terminated polybutadiene (HTPB) binder. A modified Kolsky bar apparatus was used to apply controlled dynamic compression on the PBX specimens, and a high speedmore » synchrotron X-ray phase contrast imaging (PCI) setup was used to record the in situ deformation and failure in the specimens. The experiments show that synchrotron X-ray PCI provides a sufficient contrast between the HMX crystals and the doped binder, even at ultrafast recording rates. Under dynamic compression, most of the cracking in the crystals was observed to be due to the tensile stress generated by the diametral compression applied from the contacts between the crystals. Tensile stress driven cracking was also observed for some of the crystals due to the transverse deformation of the binder and superior bonding between the crystal and the binder. In conclusion, the obtained results are vital to develop improved understanding and to validate the macroscopic and mesoscopic numerical models for energetic composites so that eventually hot spot formation can be predicted.« less

Disequilibrium dihedral angles in layered intrusions: the microstructural record of fractionation

NASA Astrophysics Data System (ADS)

Holness, Marian; Namur, Olivier; Cawthorn, Grant

2013-04-01

The dihedral angle formed at junctions between two plagioclase grains and a grain of augite is only rarely in textural equilibrium in gabbros from km-scale crustal layered intrusions. The median of a population of these disequilibrium angles, Θcpp, varies systematically within individual layered intrusions, remaining constant over large stretches of stratigraphy with significant increases or decreases associated with the addition or reduction respectively of the number of phases on the liquidus of the bulk magma. The step-wise changes in Θcpp are present in Upper Zone of the Bushveld Complex, the Megacyclic Unit I of the Sept Iles Intrusion, and the Layered Series of the Skaergaard Intrusion. The plagioclase-bearing cumulates of Rum have a bimodal distribution of Θcpp, dependent on whether the cumulus assemblage includes clinopyroxene. The presence of the step-wise changes is independent of the order of arrival of cumulus phases and of the composition of either the cumulus phases or the interstitial liquid inferred to be present in the crystal mush. Step-wise changes in the rate of change in enthalpy with temperature (ΔH) of the cooling and crystallizing magma correspond to the observed variation of Θcpp, with increases of both ΔH and Θcpp associated with the addition of another liquidus phase, and decreases of both associated with the removal of a liquidus phase. The replacement of one phase by another (e.g. olivine ⇔ orthpyroxene) has little effect on ΔH and no discernible effect on Θcpp. An increase of ΔH is manifest by an increase in the fraction of the total enthalpy budget that is the latent heat of crystallization (the fractional latent heat). It also results in an increase in the amount crystallized in each incremental temperature drop (the crystal productivity). An increased fractional latent heat and crystal productivity result in an increased rate of plagioclase growth compared to that of augite during the final stages of solidification, causing a step-wise increase in Θcpp. Step-wise changes in the geometry of three-grain junctions in fully solidified gabbros thus provide a clear microstructural marker for the progress of fractionation.

Insights from the Lattice-Strain Evolution on Deformation Mechanisms in Metallic-Glass-Matrix Composites

DOE PAGES

Jia, Haoling; Zheng, Lili; Li, Weidong; ...

2015-02-18

In this paper, in situ high-energy synchrotron X-ray diffraction experiments and micromechanics-based finite element simulations have been conducted to examine the lattice-strain evolution in metallic-glass-matrix composites (MGMCs) with dendritic crystalline phases dispersed in the metallic-glass matrix. Significant plastic deformation can be observed prior to failure from the macroscopic stress–strain curves in these MGMCs. The entire lattice-strain evolution curves can be divided into elastic–elastic (denoting deformation behavior of matrix and inclusion, respectively), elastic–plastic, and plastic–plastic stages. Characteristics of these three stages are governed by the constitutive laws of the two phases (modeled by free-volume theory and crystal plasticity) and geometric informationmore » (crystalline phase morphology and distribution). The load-partitioning mechanisms have been revealed among various crystalline orientations and between the two phases, as determined by slip strain fields in crystalline phase and by strain localizations in matrix. Finally, implications on ductility enhancement of MGMCs are also discussed.« less

Effects of short-range order on electronic properties of Zr-Ni glasses as seen from low-temperature specific heat

NASA Astrophysics Data System (ADS)

Kroeger, D. M.; Koch, C. C.; Scarbrough, J. O.; McKamey, C. G.

1984-02-01

Measurements of the low-temperature specific heat Cp of liquid-quenched Zr-Ni glasses for a large number of compositions in the range from 55 to 74 at.% Zr revealed an unusual composition dependence of the density of states at the Fermi level, N(EF). Furthermore, for some compositions the variation of Cp near the superconducting transition temperature Tc indicated the presence of two superconducting phases, i.e., two superconducting transitions were detected. Comparison of the individual Tc's in phase-separated samples to the composition dependence of Tc for all of the samples suggests that amorphous phases with compositions near 60 and 66.7 at.% Zr occur. We discuss these results in terms of an "association model" for liquid alloys (due to Sommer), in which associations of unlike atoms with definite stoichiometries are assumed to exist in equilibrium with unassociated atoms. We conclude that in the composition range studied, associate clusters with the compositions Zr3Ni2 and Zr2Ni occur. In only a few cases are the clusters sufficiently large, compared with the superconducting coherence length, for separate superconducting transitions to be observed. The variation of N(EF) with composition is discussed, as well as the effects of this chemical short-range ordering on the crystallization behavior and glass-forming tendency.

The morphology of blends of linear and branched polyethylenes by small-angle neutron and x-ray scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Londono, J.D.; Wignall, G.D.; Lin, J.S.

1995-12-31

The solid-state morphology and liquid-state homogeneity of blends of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) were investigated by small-angle neutron and x-ray scattering (SANS and SAXS). The solid state morphology was investigated as a function of composition and cooling rate from the melt. After slow cooling, the evidence indicated that the mixtures were either completely (HDPE-rich blends) or almost completely (LDPE-rich blends) phase separated into separate HDPE and LDPE lamellae over the whole compositional range. In contrast, for rapidly quenched blends the components are extensively co-crystallized for all concentrations, though the SANS data indicated that the branched component hadmore » a tendency to be preferentially located in the inter-lamellar regions. In the liquid state, the blends were homogeneous at all compositions, showing that the solid state morphology is not determined by the melt structure, but is a function of the crystallization kinetics. Further evidence for blend homogeneity in the liquid is presented. In particular the authors examine the hypothesis that a phase separated mixture might give a scattering pattern similar to a homogeneous blend if the domain sizes were larger than the maximum spatial resolution of the SANS experiment (D > 2{pi}/Q{sub min} {approximately} 2,000 {angstrom}). In this scenario, the differential scattering cross section d{Sigma}/d{Omega}(Q) {approximately} Q{sup {minus}2}, though phase separation decreases the cross section in this Q-range with respect to the homogeneous blend. For HDPE/LDPE blends in the melt, this decrease in intensity was not observed, thus ruling out the possibility of phase separation.« less

Modulation of calcium oxalate dihydrate growth by selective crystal-face binding of phosphorylated osteopontin and polyaspartate peptide showing occlusion by sectoral (compositional) zoning.

PubMed

Chien, Yung-Ching; Masica, David L; Gray, Jeffrey J; Nguyen, Sarah; Vali, Hojatollah; McKee, Marc D

2009-08-28

Calcium oxalate dihydrate (COD) mineral and the urinary protein osteopontin/uropontin (OPN) are commonly found in kidney stones. To investigate the effects of OPN on COD growth, COD crystals were grown with phosphorylated OPN or a polyaspartic acid-rich peptide of OPN (DDLDDDDD, poly-Asp(86-93)). Crystals grown with OPN showed increased dimensions of the {110} prismatic faces attributable to selective inhibition at this crystallographic face. At high concentrations of OPN, elongated crystals with dominant {110} faces were produced, often with intergrown, interpenetrating twin crystals. Poly-Asp(86-93) dose-dependently elongated crystal morphology along the {110} faces in a manner similar to OPN. In crystal growth studies using fluorescently tagged poly-Asp(86-93) followed by imaging of crystal interiors using confocal microscopy, sectoral (compositional) zoning in COD was observed resulting from selective binding and incorporation (occlusion) of peptide exclusively into {110} crystal sectors. Computational modeling of poly-Asp(86-93) adsorption to COD {110} and {101} surfaces also suggests increased stabilization of the COD {110} surface and negligible change to the natively stable {101} surface. Ultrastructural, colloidal-gold immunolocalization of OPN by transmission electron microscopy in human stones confirmed an intracrystalline distribution of OPN. In summary, OPN and its poly-Asp(86-93) sequence similarly affect COD mineral growth; the {110} crystallographic faces become enhanced and dominant attributable to {110} face inhibition by the protein/peptide, and peptides can incorporate into the mineral phase. We, thus, conclude that the poly-Asp(86-93) domain is central to the OPN ability to interact with the {110} faces of COD, where it binds to inhibit crystal growth with subsequent intracrystalline incorporation (occlusion).

Characterisation of a garnet population from the Sikkim Himalaya: implications for the mechanisms and rates of porphyroblast crystallisation

NASA Astrophysics Data System (ADS)

George, Freya; Gaidies, Fred

2016-04-01

Analysis of porphyroblast distribution in metamorphic rocks yields insight into the processes controlling metamorphic reaction rates. By coupling this textural record with microprobe analysis and phase-equilibria and diffusion modelling, a detailed view of the nucleation and growth history of metamorphic minerals can be obtained. In this study, we comprehensively characterise the 3D distribution and compositional variation of a garnet population in a garnet-grade pelitic schist of the Lesser Himalayan Sequence (Sikkim), in order to investigate both the rates and kinetic controls of porphyroblastic crystallisation. Quantification of the size, shape and spatial distribution of garnet using high-resolution μ-computed X-ray tomography and statistical analysis reveals a log-normal crystal size distribution, systematic variation of aspect ratio with crystal size, and a significantly clustered garnet texture in the study sample. The latter is indicative of interface-controlled nucleation and growth, with nucleation sites controlled principally by a heterogeneous precursor assemblage. At length-scales less than 0.7 mm, there is evidence for adjacent grains that are on average smaller than the mean size of the population; this minor ordering is attributed to secondary redistribution of porphyroblast centers and reduction of crystal sizes due to syn-kinematic growth and resorption, respectively. Geochemical traverses through centrally sectioned garnet crystals of variable size highlight several features: (1) core compositions of even the smallest crystals preserve primary prograde growth zonation, with little evidence for diffusional modification in any crystal size; (2) rim compositions are within error between grains, suggestive of sample-scale equilibration of the growth medium at the time of cessation of crystallisation; (3) different grains of equal radii display equivalent compositional zoning; and (4) gradients of compositional profiles display a steepening trend in progressively smaller grain sizes, converse to anticipated trends based on classic kinetic crystallisation theory. The observed systematic behaviour is interpreted to reflect interface-controlled rates of crystallisation, with a decrease in the rate of crystal growth of newly nucleated grains as the crystallisation interval proceeds. Numerical simulations of garnet growth successfully reproduce observed core and rim compositions, and simulations of intracrystalline diffusion yield rapid heating/cooling rates along the P-T path, in excess of 100 °C/Ma. Radial garnet crystallisation is correspondingly rapid, with minimum growth rates of 1.5 mm/Ma in the smallest crystals. Simulations suggest progressive nucleation of new generations of garnet occurred with an exponentially decreasing frequency along the prograde path; however, measured gradients indicate that core compositions developed more slowly than predicted by the model, potentially resulting in a more evenly distributed pattern of nucleation.

A density-functional study of the phase diagram of cementite-type (Fe,Mn)3C at absolute zero temperature.

PubMed

Von Appen, Jörg; Eck, Bernhard; Dronskowski, Richard

2010-11-15

The phase diagram of (Fe(1-x) Mn(x))(3)C has been investigated by means of density-functional theory (DFT) calculations at absolute zero temperature. The atomic distributions of the metal atoms are not random-like as previously proposed but we find three different, ordered regions within the phase range. The key role is played by the 8d metal site which forms, as a function of the composition, differing magnetic layers, and these dominate the physical properties. We calculated the magnetic moments, the volumes, the enthalpies of mixing and formation of 13 different compositions and explain the changes of the macroscopic properties with changes in the electronic and magnetic structures by means of bonding analyses using the Crystal Orbital Hamilton Population (COHP) technique. 2010 Wiley Periodicals, Inc.

Mineral chemistry indicates the petrogenesis of rhyolite from the southwestern Okinawa Trough

NASA Astrophysics Data System (ADS)

Chen, Zuxing; Zeng, Zhigang; Wang, Xiaoyuan; Zhang, Yuxiang; Yin, Xuebo; Chen, Shuai; Ma, Yao; Li, Xiaohui; Qi, Hanyan

2017-12-01

To reveal the petrogenesis of rhyolite from the southwestern Okinawa Trough, the mineral chemistry of plagioclase, orthopyroxene, amphibole, quartz and Fe-Ti oxide phenocrysts were analyzed using an electron microprobe, and in suit Sr and Ba contents of plagioclase analysed by LA-ICPMS were chosen for fingerprinting plagioclases of different provenances. Results indicate an overall homogeneous composition for each of the mineral phases except for plagioclase phenocrysts which have a wide range of composition (An=39 88). Plagioclase crystals characterized by An contents of >70 are not in equilibrium with their whole-rock compositions, and coarse-sieved plagioclase phenocryst interiors record high An contents (>70) and Sr/Ba ratios (>7), which are similar to the those of plagioclase crystals in basalt. Therefore, these crystals must have been introduced to the rhyolitic magma from a more mafic source. Equilibrium temperatures estimated using orthopyroxene-liquid, iron-titanium oxide, titanium-in-quartz and amphibole geothermometers show consistent values ranging from 792 to 869°C. The equilibrium pressure calculated using amphibole compositions is close to 121 MPa which corresponds to an approximate depth of 4 km. The fO2 conditions estimated from Fe-Ti oxides and amphiboles plot slightly above the NNO buffer, which indicates that the rock formed under more oxidized conditions. Our results suggests that petrogenesis of the rhyolite due to basaltic magma ascend with the high An and Sr/Ba plaigoclases from deep magma chamber into the shallow chamber where the fractional crystallization and crustal assimilation happened. It also indicates that a two-layer magma chamber structure may occur under the southwestern Okinawa Trough.

Petrology and Geochemistry of D'Orbigny, Geochemistry of Sahara 99555, and the Origin of Angrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Killgore, Marvin; Lee, Michael T.

2001-01-01

We have done detailed petrologic study of the angrite, D'Orbigny, and geochemical study of it and Sahara 99555. D'Orbigny is an igneous-textured rock composed of Ca-rich olivine, Al-Ti-diopside-hedenbergite, subcalcic kirschsteinite, two generations of hercynitic spinel and anorthite, with the mesostasis phases ulv6spinel, Ca-phosphate, a silicophosphate phase and Fe-sulfide. We report an unknown Fe-Ca-Al-Ti-silicate phase in the mesostasis not previously found in angrites. One hercynitic spinel is a large, rounded homogeneous grain of a different composition than the euhedral and zoned grains. We believe the former is a xenocryst, the first such described from angrites. The mafic phases are highly zoned; mg# of cores for olivine are approx.64, and for clinopyroxene approx.58, and both are zoned to Mg-free rims. The Ca content of olivine increases with decreasing mg#, until olivine with approx.20 mole% Ca is overgrown by subcalcic kirschsteinite with Ca approx.30-35 mole%. Detailed zoning sequences in olivine-subcalcic kirschsteinite and clinopyroxene show slight compositional reversals. There is no mineralogic control that can explain these reversals, and we believe they were likely caused by local additions of more primitive melt during crystallization of D'Orbigny. D'Orbigny is the most ferroan angrite with a bulk rock mg# of 32. Compositionally, it is virtually identical to Sahara 99555; the first set of compositionally identical angrites. Comparison with the other angrites shows that there is no simple petrogenetic sequence, partial melting with or without fractional crystallization, that can explain the angrite suite. Angra dos Reis remains a very anomalous angrite. Angrites show no evidence for the brecciation, shock, or impact or thermal metamorphism that affected the HED suite and ordinary chondrites. This suggests the angrite parent body may have followed a fundamentally different evolutionary path than did these other parent bodies.

The fabrication and visible-near-infrared optical modulation of vanadium dioxide/silicon dioxide composite photonic crystal structure

NASA Astrophysics Data System (ADS)

Liang, Jiran; Li, Peng; Song, Xiaolong; Zhou, Liwei

2017-12-01

We demonstrated a visible and near-infrared light tunable photonic nanostructure, which is composed of vanadium dioxide (VO2) thin film and silicon dioxide (SiO2) ordered nanosphere arrays. The vanadium films were sputtered on two-dimensional (2D) SiO2 sphere arrays. VO2 thin films were prepared by rapid thermal annealing (RTA) method with different oxygen flow rates. The close-packed VO2 shell formed a continuous surface, the composition of VO2 films in the structure changed when the oxygen flow rates increased. The 2D VO2/SiO2 composite photonic crystal structure exhibited transmittance trough tunability and near-infrared (NIR) transmittance modulation. When the oxygen flow rate increased from 3 slpm to 4 slpm, the largest transmittance trough can be regulated from 904 to 929 nm at low temperature, the transmittance troughs also appear blue shift when the VO2 phase changes from insulator to metal. The composite nanostructure based on VO2 films showed visible transmittance tunability, which would provide insights into the glass color changing in smart windows.

Nanostructured Crystals of Fluorite Phases Sr1 - x R x F2 + x and Their Ordering: 12. Influence of Structural Ordering on the Fluorine-Ion Conductivity of Sr0.667 R 0.333F2.333 Alloys ( R = Tb or Tm) at Their Annealing

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Karimov, D. N.; Sul'yanova, E. A.; Sobolev, B. P.

2018-01-01

The ionic conductivity of Sr0.667 R 0.333F2.333 alloys (rational Sr2 RF7 compositions) in SrF2- RF3 systems ( R = Tb or Tm), prepared by spontaneous crystallization, has been investigated for the "as-grown" state and after annealing in CF4 at 900 ± 20°C for 96 h. As-grown samples of both compositions, prepared by fast (200°C/min) melt crystallization, exhibit partial (nonequilibrium) ordering, which increases from Tb to Tm. Annealing of Sr0.667 R 0.333F2.333 alloys yields strong ordering (equilibrium for the annealing temperatures) of the fluorite structure (CaF2 type, sp. gr. Fm3̅ m, Z = 4) at the formation of t-Sr2 RF7 tetragonal compound (sp. gr. I4/ m, Z = 30). It is established that ordering of the alloy fluorite structure reduces the fluorine-ion conductivity. After the annealing, the conductivity of Sr0.667R0.333F2.333 alloys with the initial (nonequilibrium) ordering stage of t-Sr2 RF7 phases with almost complete (equilibrium) ordering decreases by a factor of 3-4.5.

Basalt generation at the Apollo 12 site. Part 2: Source heterogeneity, multiple melts, and crustal contamination

NASA Technical Reports Server (NTRS)

Neal, Clive R.; Hacker, Matthew D.; Snyder, Gregory A.; Taylor, Lawrence A.; Liu, Yun-Gang; Schmitt, Roman A.

1994-01-01

The petrogenesis of Apollo 12 mare basalts has been examined with emphasis on trace-element ratios and abundances. Vitrophyric basalts were used as parental compositions for the modeling, and proportions of fractionating phases were determined using the MAGFOX prograqm of Longhi (1991). Crystal fractionation processes within crustal and sub-crustal magma chambers are evaluated as a function of pressure. Knowledge of the fractionating phases allows trace-element variations to be considered as either source related or as a product of post-magma-generation processes. For the ilmenite and olivine basalts, trace-element variations are inherited from the source, but the pigeonite basalt data have been interpreted with open-system evolution processes through crustal assimilation. Three groups of basalts have been examined: (1) Pigeonite basalts-produced by the assimilation of lunar crustal material by a parental melt (up to 3% assimilation and 10% crystal fractionation, with an 'r' value of 0.3). (2) Ilmenite basalts-produced by variable degrees of partial melting (4-8%) of a source of olivine, pigeonite, augite, and plagioclase, brought together by overturn of the Lunar Magma Ocean (LMO) cumulate pile. After generation, which did not exhaust any of the minerals in the source, these melts experienced closed-system crystal fractionation/accumulation. (3) Olivine basalts-produced by variable degrees of partial melting (5-10%) of a source of olivine, pigeonite, and augite. After generation, again without exhausting any of the minerals in the source, these melts evolved through crystal accumulation. The evolved liquid counterparts of these cumulates have not been sampled. The source compositions for the ilmenite and olivine basalts were calculated by assuming that the vitrophyric compositions were primary and the magmas were produced by non-modal batch melting. Although the magnitude is unclear, evaluation of these source regions indicates that both be composed of early- and late-stage Lunar Magma Ocean (LMO) cumulates, requiring an overturn of the cumulate pile.

The Role of Magma Mixing in Creating Magmatic Diversity

NASA Astrophysics Data System (ADS)

Davidson, J. P.; Collins, S.; Morgan, D. J.

2012-12-01

Most magmas derived from the mantle are fundamentally basaltic. An assessment of actual magmatic rock compositions erupted at the earth's surface, however, shows greater diversity. While still strongly dominated by basalts, magmatic rock compositions extend to far more differentiated (higher SiO2, LREE enriched) compositions. Magmatic diversity is generated by differentiation processes, including crystal fractionation/ accumulation, crustal contamination and magma mixing. Among these, magma mixing is arguably inevitable in magma systems that deliver magmas from source-to-surface, since magmas will tend to multiply re-occupy plumbing systems. A given mantle-derived magma type will mix with any residual magmas (and crystals) in the system, and with any partial melts of the wallrock which are generated as it is repeatedly flushed through the system. Evidence for magma mixing can be read from the petrography (identification of crystals derived from different magmas), a technique which is now well-developed and supplemented by isotopic fingerprinting (1,2) As a means of creating diversity, mixing is inevitably not efficient as its tendency is to blend towards a common composition (i.e. converging on homogeneity rather than diversity). It may be surprising then that many systems do not tend to homogenise with time, meaning that the timescales of mixing episodes and eruption must be similar to external magma contributions of distinct composition (recharge?). Indeed recharge and mixing/ contamination may well be related. As a result, the consequences of magma mixing may well bear on eruption triggering. When two magmas mix, volatile exsolution may be triggered by retrograde boiling, with crystallisation of anhydrous phase(s) in either of the magmas (3) or volatiles may be generated by thermal breakdown of a hydrous phase in one of the magmas (4). The generation of gas pressures in this way probably leads to geophysical signals too (small earthquakes). Recent work pulling these ideas together has suggested that mixing generates volatile release accompanied by geophysical signals, and the petrographic fingerprints of crystal exchange. Crystal overgowths then reflect the composition of the hybrid magma. The compositional profile (overgrowth) can then be inverted provided T and diffusivity are known. This gives a potential characteristic timescales between mixing and eruption (calculated for instance as ~17 years at Vesuvius around the time of Pompeii (5) and 7 weeks at Nea Kameni, Santorini (6)(, These characteristic timescales may represent the time between mixing and eruption and may therefore be useful in prediction, especially so if there is a geophysical signal (earthquakes) associated with it. (1) Davidson, J.P., Morgan, D.J., Charlier, B.L.A., Harlou, R. and Hora, J.M., 2007. Ann. Rev. Earth Planet. Sci. 35, 273-311, (2) Davidson, J.P., Tepley, FJ III, Palacz, Z., and Main, S., 2001, Earth and Planetary Science Lett., 182, 427-44 (3) Pallister, J.S., Hoblitt, R.P, Reyes, A.G., 1992. Nature 356, 426 - 428 (4) Feeley, T.C. and Sharp, Z.D., 1998. Geology, v. 24 no. 11 p. 1021-1024 (5) Morgan, D.J., Blake, S., Rogers, N.W., De Vivo, B., Rolandi, G. and Davidson, J.P., 2006. Geology 34, 845-848 (6) Martin, V.M., Morgan, D.J., Jerram, D.A., Caddick, M.J., Prior, D and Davidson, J.P., 2008. Science, 321, 1178.

Evolution of the Campanian Ignimbrite Magmatic System I: Constraints on Compositional Zonation and Eruption Probability Imposed By Phase Equilibria

NASA Astrophysics Data System (ADS)

Fowler, S.; Spera, F.; Bohrson, W.; Belkin, H.; Devivo, B.

2005-12-01

The eruption and deposition of the ~39.3 ka Campanian Ignimbrite (CI), a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite, is the dominant event in the history of the Campi Flegrei volcanic field near Naples, Italy. In an effort to comprehend its petrological evolution, we have conducted ~~110 MELTS (Ghiorso, 1997) phase equilibria simulations of the major element evolution of parental CI magma. The goals of this work are to approximate oxygen fugacity (fO2), initial dissolved water content and pressure at which isobaric closed system fractional crystallization of parental melt most accurately captures the observed liquid line of descent and to study the implications of heat extraction from parental CI magma with respect to the origin of compositional zonation and the probability of explosive eruption. Although the CI magma body did not evolve as a perfectly closed system, this assumption allows quantitative insight into magma-host rock mass exchange using trace element and isotopic data (see companion contribution by Bohrson et al.). The parental melt composition was reconstructed using data for melt inclusions trapped within CI clinopyroxene phenocrysts reported by Webster et al. (2003), while allowing for reaction between parental melt and clinopyroxene host. The inferred parental melt is a basaltic trachyandesite. The search space for pressure, (fO2) and initial dissolved H2O was 0.1-0.5 in 0.05 GPa increments, QFM-1 to QFM+3 and 1, 2 and 3 wt. % H2O, respectively. The criteria used to judge the quality of a simulation include correspondence of the MELTS prediction with CI liquid and phenocryst compositions. Results indicate that a good first-order model involves evolution from a basaltic trachyandesite parent by isobaric (~0.15 GPa) crystal fractionation initially containing ~3 wt% dissolved H2O along the QFM+1 buffer. H2O first saturates at 1127°C at 0.15 GPa when the dissolved water content is ~4 wt %. A striking result is the discovery of a pseudo-invariant point at ~883°C (Tip) and 0.15 GPa. The fraction of melt changes abruptly from ~0.5 to ~0.1 at Tip due to the simultaneous crystallization of alkali feldspar, plagioclase, spinel, biotite and apatite. At Tip, there is a dramatic decrease in the viscosity of melt (by a factor of four) and magma density (~5%) and an increase in the dissolved H2O content of the melt (from 4.4-5.1 wt%) and in the volume fraction,θ, of supercritical fluid in the multiphase system. In particular, θ increases from ~0.05 at 885°C to ~0.6 at 882°C. The liquid composition also changes discontinuously at Tip with Si, Na, and H2O increasing and K and Al decreasing as temperature falls below Tip. The marked variations in composition and properties of volatile-saturated melt and magma were the trigger that led to the catastrophic eruption and formation of the compositionally-zoned CI magma. Because phase equilibria modeling provides information on the enthalpy changes associated with fractional crystallization and because the dimensions of the CI magma chamber and heat extraction rate can be approximated, a time scale for CI magmatic evolution can be derived. The estimated crystallization duration (τ) is10-100 ka and 75% of τ is spent at or near Tip.

New Experimental Constraints on Crystallization Differentiation in a Deep Magma Ocean

NASA Astrophysics Data System (ADS)

Walter, M. J.; Ito, E.; Nakamura, E.; Tronnes, R.; Frost, D.

2001-12-01

Most of Earth's mass probably accreted as a consequence of numerous impacts between large bodies and proto-Earth, and a giant impact with a Mars-sized object is the most plausible explanation for a Moon forming event. 1 Physical models show that large impacts would have caused high-degrees of melting and a global magma ocean. 2 Crystallization differentiation in a deep magma ocean could impart stratification in the solidified mantle, forming large geochemical domains. To accurately model crystallization in a deep magma ocean the liquidus phase-relations of peridotite, as well as mineral/melt element partitioning, must be known at lower mantle conditions. Here, we report the results of liquidus experiments on fertile model peridotite compositions at 23 - 33 GPa. Experiments were performed in 6/8-type multi-anvil apparatus using carbide and sintered-diamond second-stage anvils with 4 and 2 mm truncations, respectively. Samples were encapsulated by either graphite or Re. High-temperatures were generated using LaCrO3 or Re furnaces, and temperatures were held from 2 to 50 minutes at 2300 - 2500 C. Run products were analyzed for major and trace elements using EPMA and SIMS. At 23 GPa the liquidus phase is majorite, followed closely down temperature by ferropericlase (Fp) and Mg-perovskite (Mg-Pv). At 24 GPa the liquidus phase has changed to Fp, followed closely by majorite and Mg-Pv. Ca-perovskite (Ca-Pv) is present only at much lower temperatures close to the solidus. At approximately 31 GPa Mg-Pv is the liquidus phase followed down-temperature by Fp then Ca-Pv. At ~ 33 GPa Ca-Pv crystallizes closer to the liquidus, within about 50 C, at a similar temperature to Fp. Thus, important phases crystallizing in a deep magma ocean are Mg-Pv, Ca-Pv and Fp. Crystallization models based on major element partitioning show that only very modest amounts of crystal separation of a Mg-Pv + Fp assemblage can be tolerated before Ca/Al, Al/Ti and Ca/Ti ratios become unrealistic for estimates of primitive upper mantle (PUM). 3 However, even small amounts of Ca-Pv in the crystal assemblage effectively buffer these ratios at values close to the starting composition (e.g. chondritic). Further, based on our new trace element partitioning data, models involving considerable Mg-Pv fractionation generally show poor matches with model PUM. For example, model PUM has sub-chondritic REE/Ti, whereas these ratios increase considerably during Mg-Pv crystallization. Notable exceptions are super-chondritic Zr/Ti, chondritic Sr/Ti, and sub-chondritic Zr/Nb and Sm/Yb ratios, all of which are well matched by considerable Mg-Pv crystallization. Although trace element D's for Ca-Pv are not yet measured quantitatively, the observed affinity of Ca-Pv for REE could conceivably account for the the sub-chondritic REE/Ti ratios in PUM. Ca-Pv also concentrates K, and could be an important source of heat from radioactive decay in the lower mantle. 1. Canup, R. and Agnor, C., Origin of the Earth and Moon, Righter and Canup, eds., U. Arizona Press, 113-144, 2000. 2. Melosh, H., Origin of the Earth, Newsom and Jones, eds., Oxford Press, 69-84, 1990. 3. McFarlane, E. et al., Geochimica et Cosmochimica Acta, 5161-5172, 1994.

Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

DOE PAGES

Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

2015-01-31

Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

Hydrothermal synthesis of free-template zeolite T from kaolin

NASA Astrophysics Data System (ADS)

Arshad, Sazmal E.; Yusslee, Eddy F.; Rahman, Md. Lutfor; Sarkar, Shaheen M.; Patuwan, Siti Z.

2017-12-01

Free-template zeolite T crystals were synthesized via hydrothermal synthesis by utilizing the activated kaolin as silica and alumina source, with the molar composition of 1 SiO2: 0.04 Al2O3: 0.26 Na2O: 0.09 K2O: 14 H2O. Observation of the formation of free-template zeolite crystals were done at temperature 90°C, 100 °C and 110 °C respectively. It was therefore determined that during the 120 h of the synthesis at 90 °C, zeolite T nucleated and formed a first competitive phase with zeolite L. As temperature increases to 100 °C, zeolite T presented itself as a major phase in the system at time 168 h. Subsequently, development of Zeolite T with second competitive phase of zeolite W was observed at temperature 110 °C. In this study, XRD and SEM instruments were used to monitor the behavior of zeolite T crystals with respect of temperature and time. By using natural resource of kaolin clay as a starting material, this paper hence aims to provide new findings in synthesis of zeolite T using low energy consumption and low production cost.

New milarite/osumilite-type phase formed during ancient glazing of an Egyptian scarab

NASA Astrophysics Data System (ADS)

Artioli, G.; Angelini, I.; Nestola, F.

2013-02-01

A scarab found in grave 25 of the Monte Prama necropolis, near Cabras, Oristano, Sardinia, is of special importance for the archaeological interpretation and dating of this important archaeological site. The object has been misinterpreted in the past as composed by bone: recent archaeometric analyses showed that it is a glazed steatite of Egyptian origin and that the altered surface contains interesting phases crystallized during the high-temperature interaction of the Mg-rich talc core with the alkali-rich glass used for glazing. A novel single crystal X-ray diffraction analysis of one of the phases indicates that it is a new compound having the milarite-osumilite structure type, with a peculiar composition close to (Na1.52K0.12□0.36)(Mg3)(Mg1.72Cu0.16Fe0.12)(Si11.4Al0.6)O30, not reported for naturally occurring minerals. The structural and crystal chemical features of the compound, together with the known high-temperature stability of the series, allow a complete interpretation of the glazing process and conditions, based on direct application of the glaze on the steatite core with subsequent treatment at temperatures above 1000 °C.

Oxygen isotope composition of mafic magmas at Vesuvius

NASA Astrophysics Data System (ADS)

Dallai, L.; Cioni, R.; Boschi, C.; D'Oriano, C.

2009-12-01

The oxygen isotope composition of olivine and clinopyroxene from four plinian (AD 79 Pompeii, 3960 BP Avellino), subplinian (AD 472 Pollena) and violent strombolian (Middle Age activity) eruptions were measured to constrain the nature and evolution of the primary magmas of the last 4000 years of Mt. Vesuvius activity. A large set of mm-sized crystals was accurately separated from selected juvenile material of the four eruptions. Crystals were analyzed for their major and trace element compositions (EPMA, Laser Ablation ICP-MS), and for 18O/16O ratios. As oxygen isotope composition of uncontaminated mantle rocks on world-wide scale is well constrained (δ18Oolivine = 5.2 ± 0.3; δ18Ocpx = 5.6 ± 0.3 ‰), the measured values can be conveniently used to monitor the effects of assimilation/contamination of crustal rocks in the evolution of the primary magmas. Instead, typically uncontaminated mantle values are hardly recovered in Italian Quaternary magmas, mostly due to the widespread occurrence of crustal contamination of the primary magmas during their ascent to the surface (e.g. Alban Hills, Ernici Mts., and Aeolian Islands). Low δ18O values have been measured in olivine from Pompeii eruption (δ18Oolivine = 5.54 ± 0.03‰), whereas higher O-compositions are recorded in mafic minerals from pumices or scoria of the other three eruptions. Measured olivine and clinopyroxene share quite homogeneous chemical compositions (Olivine Fo 85-90 ; Diopside En 45-48, respectively), and represent phases crystallized in near primary mafic magmas, as also constrained by their trace element compositions. Data on melt inclusions hosted in crystals of these compositions have been largely collected in the past demonstrating that they crystallized from mafic melt, basaltic to tephritic in composition. Published data on volatile content of these melt inclusions reveal the coexistence of dissolved water and carbon dioxide, and a minimum trapping pressure around 200-300 MPa, suggesting that crystal growth possibly occurred during magma ascent from the source region or in a shallow reservoir at about 8-10 km depth. Recently, experimental data have suggested massive carbonate assimilation (up to about 20%) to derive potassic alkali magmas from trachybasaltic melts. Accordingly, the δ18O variability and the trace element contents of the studied minerals suggest possible contamination of primary melts by an O-isotope enriched, REE-poor contaminant like the limestone of Vesuvius basement. The δ18Oolivine and δ18Ocpx of the studied minerals define variable degrees of carbonate assimilation and magma crystallization for the different eruptions, and possibly within the same eruption, and show evidence of oxygen isotope equilibrium at high temperature. However, energy-constrained AFC model suggest that carbonate contamination was limited. On the basis of our data, we suggest that interaction between magma and a fluxing, decarbonation-derived CO2 fluid may be partly accounted for the measured O-isotope compositions.

Moisture-Induced Amorphous Phase Separation of Amorphous Solid Dispersions: Molecular Mechanism, Microstructure, and Its Impact on Dissolution Performance.

PubMed

Chen, Huijun; Pui, Yipshu; Liu, Chengyu; Chen, Zhen; Su, Ching-Chiang; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Foster, Kimberly; Gudmundsson, Olafur; Qian, Feng

2018-01-01

Amorphous phase separation (APS) is commonly observed in amorphous solid dispersions (ASD) when exposed to moisture. The objective of this study was to investigate: (1) the phase behavior of amorphous solid dispersions composed of a poorly water-soluble drug with extremely low crystallization propensity, BMS-817399, and PVP, following exposure to different relative humidity (RH), and (2) the impact of phase separation on the intrinsic dissolution rate of amorphous solid dispersion. Drug-polymer interaction was confirmed in ASDs at different drug loading using infrared (IR) spectroscopy and water vapor sorption analysis. It was found that the drug-polymer interaction could persist at low RH (≤75% RH) but was disrupted after exposure to high RH, with the advent of phase separation. Surface morphology and composition of 40/60 ASD at micro-/nano-scale before and after exposure to 95% RH were also compared. It was found that hydrophobic drug enriched on the surface of ASD after APS. However, for the 40/60 ASD system, the intrinsic dissolution rate of amorphous drug was hardly affected by the phase behavior of ASD, which may be partially attributed to the low crystallization tendency of amorphous BMS-817399 and enriched drug amount on the surface of ASD. Intrinsic dissolution rate of PVP decreased resulting from APS, leading to a lower concentration in the dissolution medium, but supersaturation maintenance was not anticipated to be altered after phase separation due to the limited ability of PVP to inhibit drug precipitation and prolong the supersaturation of drug in solution. This study indicated that for compounds with low crystallization propensity and high hydrophobicity, the risk of moisture-induced APS is high but such phase separation may not have profound impact on the drug dissolution performance of ASDs. Therefore, application of ASD technology on slow crystallizers could incur low risks not only in physical stability but also in dissolution performance. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Otoconia biogenesis, phylogeny, composition and functional attributes

NASA Technical Reports Server (NTRS)

Fermin, C. D.; Lychakov, D.; Campos, A.; Hara, H.; Sondag, E.; Jones, T.; Jones, S.; Taylor, M.; Meza-Ruiz, G.; Martin, D. S.

1998-01-01

This work consolidates data about these interesting organic crystals of vertebrate inner ears. It addresses 5 aspects of inner ear otoliths not completely understood to date: 1) embryological data that explains the formation of the crystals, 2) the significance of the organic and the inorganic phase of the otolith and the changing patterns of otoconia formation along the evolutionary tree, 3) otoliths contribution for detecting linear acceleration, 4) the effect that altered gravity and aminoglycosides have on the development and adult shape of the crystals, and the evolutionary significance of a changing shape of the crystals from primitive forms (lamprey) to high vertebrate birds and mammals is discussed, 5) functional attributes of the otolithic organs and morphological modifications of the otoliths by physical and chemical insults are presented with an extensive discussion of the most relevant literature published and available to us.

Preparation and investigation of Ge-S-I glasses for infrared fiber optics

NASA Astrophysics Data System (ADS)

Velmuzhov, A. P.; Sukhanov, M. V.; Plekhovich, A. D.; Snopatin, G. E.; Churbanov, M. F.; Iskhakova, L. D.; Ermakov, R. P.; Kotereva, T. V.; Shiryaev, V. S.

2016-02-01

Glass samples of [GeSx]90I10 (x = 1.5, 1.7, 2.0, 2.3, 2.45, 2.6) compositions were prepared, and some their thermal, optical properties as well as tendency to crystallization were investigated. The compositional dependences of glass transition temperature, volume fraction of crystallized phase and activation energy of glass formation (Eg) have nonmonotonic character with a maximum for [GeS2.0]90I10 glass. Glasses of 85.8GeS2-14.2GeI4 and [GeS1.5]90I10 compositions are identified as promising for preparation of optical fiber. For the first time, Ge-S-I glass fibers were produced. Minimum optical losses in 85.8GeS2-14.2GeI4 glass fiber were 2.7 dB/m at a wavelength of 5.1 μm, and that in [GeS1.5]90I10 glass fiber were 14.5 dB/m at 5.5 μm.

High compositional homogeneity of CdTe{sub x}Se{sub 1−x} crystals grown by the Bridgman method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy, U. N.; Bolotnikov, A. E.; Camarda, G. S.

2015-02-01

We obtained high-quality CdTe{sub x}Se{sub 1−x} (CdTeSe) crystals from ingots grown by the vertical Bridgman technique. The compositional uniformity of the ingots was evaluated by X-ray fluorescence at BNL’s National Synchrotron Light Source X27A beam line. The compositional homogeneity was highly uniform throughout the ingot, and the effective segregation coefficient of Se was ∼1.0. This high uniformity offers potential opportunity to enhance the yield of the materials for both infrared substrate and radiation-detector applications, so greatly lowering the cost of production and also offering us the prospect to grow large-diameter ingots for use as large-area substrates and for producing highermore » efficiency gamma-ray detectors. The concentration of secondary phases was found to be much lower, by eight- to ten fold compared to that of conventional Cd{sub x}Zn{sub 1−x}Te (CdZnTe or CZT)« less

High Compositional Homogeneity of CdTe xSe 1-x Crystals Grown by the Bridgman Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roy, U. N.; Bolotnikov, A. E.; Camarda, G. S.

2015-02-03

We obtained high-quality CdTe xSe 1-x (CdTeSe) crystals from ingots grown by the vertical Bridgman technique. The compositional uniformity of the ingots was evaluated by X-ray fluorescence at BNL’s National Synchrotron Light Source X27A beam line. The resulting compositional homogeneity was highly uniform throughout the ingot, and the effective segregation coefficient of Se was ~1.0. This uniformity offers potential opportunity to enhance the yield of the materials for both infrared substrate and radiation-detector applications, so greatly lowering the cost of production and also offering us the prospect to grow large-diameter ingots for use as large-area substrates and for producing highermore » efficiency gamma-ray detectors. The concentration of secondary phases was found to be much lower, by eight- to ten fold compared to that of conventional Cd xZn 1-xTe (CdZnTe or CZT).« less

Structural, dielectric and magnetic properties of ZnFe2O4-Na0.5Bi0.5TiO3 multiferroic composites

NASA Astrophysics Data System (ADS)

Bhasin, Tanvi; Agarwal, Ashish; Sanghi, Sujata; Yadav, Manisha; Tuteja, Muskaan; Singh, Jogender; Rani, Sonia

2018-04-01

Multiferroic xNa0.5Bi0.5TiO3-(1-x)ZnFe2O4 (x=0.10, 0.20) composites were prepared by conventional solid state reaction method. Rietveld analysis of XRD data shows that samples exhibit both cubic (Fd-3m) and rhombohedral (R3c) crystal structure. Structural parameters and unit cell volume of samples vary with composition. The dielectric constant and dielectric loss (tanδ) display dispersion at low frequency due to space charge polarization and inhomogeneity in the composites. Magnetic analysis depicts the antiferromagnetic behavior of composites and magnetization is enhanced with the introduction of ferrite (ZnFe2O4) phase.

Structure and crystallization of SiO2 and B2O3 doped lithium disilicate glasses from theory and experiment.

PubMed

Erlebach, Andreas; Thieme, Katrin; Sierka, Marek; Rüssel, Christian

2017-09-27

Solid solutions of SiO 2 and B 2 O 3 in Li 2 O·2SiO 2 are synthesized and characterized for the first time. Their structure and crystallization mechanisms are investigated employing a combination of simulations at the density functional theory level and experiments on the crystallization of SiO 2 and B 2 O 3 doped lithium disilicate glasses. The remarkable agreement of calculated and experimentally determined cell parameters reveals the preferential, kinetically controlled incorporation of [SiO 4 ] and [BO 4 ] at the Li + lattice sites of the Li 2 O·2SiO 2 crystal structure. While the addition of SiO 2 increases the glass viscosity resulting in lower crystal growth velocities, glasses containing B 2 O 3 show a reduction of both viscosities and crystal growth velocities. These observations could be rationalized by a change of the chemical composition of the glass matrix surrounding the precipitated crystal phase during the course of crystallization, which leads to a deceleration of the attachment of building units required for further crystal growth at the liquid-crystal interface.

Zirconia toughened mica glass ceramics for dental restorations.

PubMed

Gali, Sivaranjani; K, Ravikumar; Murthy, B V S; Basu, Bikramjit

2018-03-01

The objective of the present study is to understand the role of yttria stabilized zirconia (YSZ) in achieving the desired spectrum of clinically relevant mechanical properties (hardness, elastic modulus, fracture toughness and brittleness index) and chemical solubility of mica glass ceramics. The glass-zirconia mixtures with varying amounts of YSZ (0, 5, 10, 15 and 20wt.%) were ball milled, compacted and sintered to obtain pellets of glass ceramic-YSZ composites. Phase analysis was carried out using X-ray diffraction and microstructural characterization with SEM revealed the crystal morphology of the composites. Mechanical properties such as Vickers hardness, elastic modulus, indentation fracture toughness and chemical solubility were assessed. Phase analysis of sintered pellets of glass ceramic-YSZ composites revealed the characteristic peaks of fluorophlogopite (FPP) and tetragonal zirconia. Microstructural investigation showed plate and lath-like interlocking mica crystals with embedded zirconia. Vickers hardness of 9.2GPa, elastic modulus of 125GPa, indentation toughness of 3.6MPa·m 1/2 , and chemical solubility of 30μg/cm 2 (well below the permissible limit) were recorded with mica glass ceramics containing 20wt.% YSZ. An increase in hardness and toughness of the glass ceramic-YSZ composites with no compromise on their brittleness index and chemical solubility has been observed. Such spectrum of properties can be utilised for developing a machinable ceramic for low stress bearing inlays, onlays and veneers. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Mössbauer study and magnetic properties of MgFe2O4 crystallized from the glass system B2O3/K2O/P2O5/MgO/Fe2O3

NASA Astrophysics Data System (ADS)

Shabrawy, S. El; Bocker, C.; Miglierini, M.; Schaaf, P.; Tzankov, D.; Georgieva, M.; Harizanova, R.; Rüssel, C.

2017-01-01

An iron containing magnesium borate glass with the mol% composition 51.7 B2O3/9.3 K2O /1 P2O5/27.6MgO/10.4Fe2O3was prepared by the conventional melts quenching method followed by a thermal treatment process at temperatures in the range from 530 to 604 °C.The thermally treated samples were characterized by X-ray diffraction, scanning and transmission electron microscopy. It was shown that superparamagnetic MgFe2O4 nanoparticles were formed during thermal treatment. The size of the spinel type crystals was in the range from 6 to 15 nm. Mössbauer spectra of the powdered glass ceramic samples and the extracted nanoparticles after dissolving the glass matrix in diluted acid were recorded at room temperature. The deconvolution of the spectra revealed the crystallization of two spinel phases MgFe2O4 (as a dominant phase) and superparamagnetic maghemite, γ-Fe2O3 (as a secondary phase). Room temperature magnetic measurements showed that, increasing the crystallization temperature changed the superparamagnetic behavior of the samples to ferrimagnetic behavior. The Curie temperatures of the samples were measured and showed a higher value than that of the pure bulk MgFe2O4.

Three-Dimensional Model of Holographic Formation of Inhomogeneous PPLC Diffraction Structures

NASA Astrophysics Data System (ADS)

Semkin, A. O.; Sharangovich, S. N.

2018-05-01

A three-dimensional theoretical model of holographic formation of inhomogeneous diffraction structures in composite photopolymer - liquid crystal materials is presented considering both the nonlinearity of recording and the amplitude-phase inhomogeneity of the recording light field. Based on the results of numerical simulation, the kinematics of formations of such structures and their spatial profile are investigated.

Structure and Properties of Sn2Se3, a mixed valent tin selenium compound

NASA Astrophysics Data System (ADS)

Xing, Guangzong; Li, Yuwei; Fan, Xiaofeng; Zhang, Lijun; Singh, David

Sn2Se3 is a possibly expected phase based on analogy with Sn2S3 but it has never been reported. It is of interest due to reported phase change memories using this composition using transitions between an amorphous phase and an unknown crystalline phase. We identify the crystal structure Sn2Se3 and report its properties at ambient pressure based on the ab initio evolutionary methodology for crystal structure prediction implemented in the Calypso code. We find a structure based on Sn-Se ribbons with clear Sn(II)and Sn(IV)sites similar to the structure of Sn2S3. Compared with the known phase SnSe (Pnma) +SnSe2 (P-3m1), the energy is only 2.3meV/atom higher. The electronic structure of this phase shows mixed valent tins Sn2+ and Sn4+ in this compound. A small band gap of 0.023 eV is obtained from the band structure consistent with the small resistance reported by Kyung-Min Chung et al. Work at the University of Missouri is supported by DOE through the S3TEC EFRC.

Crystallization of Yamato 980459 at 0.5 GPA: Are Residual Liquids Like QUE 94201?

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Draper, D. S.; Mercer, C.

2012-01-01

The Martian basaltic meteorites Y980459 and QUE94201 (henceforth referred to as Y98 and QUE respectively) are thought to represent magmatic liquid compositions, rather than being products of protracted crystallization and accumulation like the majority of other martian meteorites. Both meteorite compositions have been experimentally crystallized at 1 bar, and liquidus phases were found to match corresponding mineral core compositions in the meteorites, consistent with the notion that these meteorites represent bona fide melts. They also represent the most primitive and most evolved basaltic martian samples, respectively. Y98 has Mg# (molar Mg/Mg+Fe) approximates 65, and lacks plagioclase; whereas QUE has Mg# approximates 40, and lacks olivine. However they share important geochemical characteristics (e.g. superchondritic CaO/Al2O3, very high epsilon(sub Nd) and low Sr-87/Sr-87) that suggest they sample a similar highly depleted mantle reservoir. As such, they represent likely endmembers of martian magmatic liquid compositions, and it is natural to seek petrogenetic linkages between the two. We make no claim that the actual meteorites themselves share a genetic link (the respective ages rule that out); we are exploring only in general whether primitive martian liquids like Y98 could evolve to liquids resembling QUE. Both experimental and computational efforts have been made to determine if there is indeed such a link. Recent petrological models at 1 bar generated using MELTS suggest that a QUE-like melt can be derived from a parental melt with a Y98 composition. However, experimental studies at 1 bar have been less successful at replicating this progression. Previous experimental crystallization studies of Y98 by our group at 0.5 GPa have produced melt compositions approaching that of QUE, although these results were complicated by the presence of small, variable amounts of H2O in some of the runs owing to the use of talc/pyrex experimental assemblies. Therefore we have repeated the four experiments, augmented with additional runs, all using BaCO3 cell assemblies, which are devoid of water, and these new experiments supersede those reported earlier. Here we report results of experiments simulating equilibrium crystallization; fractional crystallization experiments are currently underway.

Effect of Sb on physical properties and microstructures of laser nano/amorphous-composite film

NASA Astrophysics Data System (ADS)

Li, Jia-Ning; Gong, Shui-Li; Sun, Mei; Shan, Fei-Hu; Wang, Xi-Chang; Jiang, Shuai

2013-11-01

A nano/amorphous-composite film was fabricated by laser cladding (LC) of the Co-Ti-B4C-Sb mixed powders on a TA15 alloy. Such film mainly consisted of Ti-Al, Co-Ti, Co-Sb intermetallics, TiC, TiB2, TiB, and the amorphous phases. Experimental results indicated that the crystal systems of TiB2 (hexagonal)/TiC (cubic) and Sb (rhombohedral) played important role on the formation of such film. Due to the mismatch of these crystals systems and mutual immiscibility of the metallic components, Sb was not incorporated in TiB2/TiC, but formed separate nuclei during the film growth. Thus, the growth of TiB2/TiC was stopped by the Sb nucleus in such LC molten pool, so as to form the nanoscale particles.

Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.

2014-01-28

The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B{sub 2}O{sub 3}-10SiO{sub 2} were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T{sub g}) and of the maximum crystallization temperature (T{sub p}) on the heating rate was used to determine the activation energy associated with the glass transition (E{sub g}), the activation energy for crystallization (E{sub c}), and the Avrami exponent (n). X-ray diffractionmore » (XRD) revealed that barium borate (β-BaB{sub 2}O{sub 4}) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba{sub 5}Si{sub 8}O{sub 21}). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E{sub c}(χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures.« less

An inverse modeling strategy and a computer program to model garnet growth and resorption

NASA Astrophysics Data System (ADS)

Lanari, Pierre; Giuntoli, Francesco

2017-04-01

GrtMod is a computer program that allows numerical simulation of the pressure-temperature (P-T) evolution of garnet porphyroblasts based on the composition of successive growth zones preserved in natural samples. For each garnet growth stage, a new reactive bulk composition is optimized, allowing for resorption and/or fractionation of the previously crystalized garnet. The successive minimizations are performed using a heuristic search method and an objective function that quantify the amount by which the predicted garnet composition deviates from the measured values. The automated strategy of GrtMod includes a two stages optimization and one refinement stage. In this contribution, we will present several application examples. The new strategy provides quantitative estimates of the optimal P-T conditions whereas it was generally derived in a qualitatively way by using garnet isopleth intersections in equilibrium phase diagrams. GrtMod can also be used to model the evolution of the reactive bulk composition along any P-T trajectories. The results for typical MORB and metapelite compositions demonstrate that fractional crystallization models are required to derive accurate P-T information from garnet compositional zoning. GrtMod can also be used to retrieve complex garnet histories involving several stages of resorption. For instance, it has been used to model the P-T condition of garnet growth in grains from the Sesia Zone (Western Alps). The compositional variability of successive growth zones is characterized using standardized X-ray maps and the program XMapTools. Permian garnet cores crystalized under granulite facies conditions (T > 800°C and P = 6 kbar), whereas Alpine garnet rims grew at eclogite facies conditions (650°C and 16 kbar) involving several successive episodes of resorption. The model predicts that up to 50 vol% of garnet was dissolved before a new episode of garnet growth.