Tailoring the Microstructure of Sol–Gel Derived Hydroxyapatite/Zirconia Nanocrystalline Composites

PubMed Central

2011-01-01

In this study, we tailor the microstructure of hydroxyapatite/zirconia nanocrystalline composites by optimizing processing parameters, namely, introducing an atmosphere of water vapor during sintering in order to control the thermal stability of hydroxyapatite, and a modified sol–gel process that yields to an excellent intergranular distribution of zirconia phase dispersed intergranularly within the hydroxyapatite matrix. In terms of mechanical behavior, SEM images of fissure deflection and the presence of monoclinic ZrO2 content on cracked surface indicate that both toughening mechanisms, stress-induced tetragonal to monoclinic phase transformation and deflection, are active for toughness enhancement. PMID:24764458

Experiment-based modelling of grain boundary β-phase (Mg2Al3) evolution during sensitisation of aluminium alloy AA5083.

PubMed

Zhang, R; Steiner, M A; Agnew, S R; Kairy, S K; Davies, C H J; Birbilis, N

2017-06-07

An empirical model for the evolution of β-phase (Mg 2 Al 3 ) along grain boundaries in aluminium alloy AA5083 (Al-Mg-Mn) during isothermal exposures is proposed herein. Developing a quantitative understanding of grain boundary precipitation is important to interpreting intergranular corrosion and stress corrosion cracking in this alloy system. To date, complete ab initio models for grain boundary precipitation based upon fundamental principles of thermodynamics and kinetics are not available, despite the critical role that such precipitates play in dictating intergranular corrosion phenomena. Empirical models can therefore serve an important role in advancing the understanding of grain boundary precipitation kinetics, which is an approach applicable beyond the present context. High resolution scanning electron microscopy was to quantify the size and distribution of β-phase precipitates on Ga-embrittled intergranular fracture surfaces of AA5083. The results are compared with the degree of sensitisation (DoS) as judged by nitric acid mass loss testing (ASTM-G67-04), and discussed with models for sensitisation in 5xxx series Al-alloys. The work herein allows sensitisation to be quantified from an unambiguous microstructural perspective.

Nanostructures having crystalline and amorphous phases

DOEpatents

Mao, Samuel S; Chen, Xiaobo

2015-04-28

The present invention includes a nanostructure, a method of making thereof, and a method of photocatalysis. In one embodiment, the nanostructure includes a crystalline phase and an amorphous phase in contact with the crystalline phase. Each of the crystalline and amorphous phases has at least one dimension on a nanometer scale. In another embodiment, the nanostructure includes a nanoparticle comprising a crystalline phase and an amorphous phase. The amorphous phase is in a selected amount. In another embodiment, the nanostructure includes crystalline titanium dioxide and amorphous titanium dioxide in contact with the crystalline titanium dioxide. Each of the crystalline and amorphous titanium dioxide has at least one dimension on a nanometer scale.

Use of additives to improve microstructures and fracture resistance of silicon nitride ceramics

DOEpatents

Becher, Paul F [Oak Ridge, TN; Lin, Hua-Tay [Oak Ridge, TN

2011-06-28

A high-strength, fracture-resistant silicon nitride ceramic material that includes about 5 to about 75 wt-% of elongated reinforcing grains of beta-silicon nitride, about 20 to about 95 wt-% of fine grains of beta-silicon nitride, wherein the fine grains have a major axis of less than about 1 micron; and about 1 to about 15 wt-% of an amorphous intergranular phase comprising Si, N, O, a rare earth element and a secondary densification element. The elongated reinforcing grains have an aspect ratio of 2:1 or greater and a major axis measuring about 1 micron or greater. The elongated reinforcing grains are essentially isotropically oriented within the ceramic microstructure. The silicon nitride ceramic exhibits a room temperature flexure strength of 1,000 MPa or greater and a fracture toughness of 9 MPa-m.sup.(1/2) or greater. The silicon nitride ceramic exhibits a peak strength of 800 MPa or greater at 1200 degrees C. Also included are methods of making silicon nitride ceramic materials which exhibit the described high flexure strength and fracture-resistant values.

Multi-scale modeling of microstructure dependent intergranular brittle fracture using a quantitative phase-field based method

DOE PAGES

Chakraborty, Pritam; Zhang, Yongfeng; Tonks, Michael R.

2015-12-07

In this study, the fracture behavior of brittle materials is strongly influenced by their underlying microstructure that needs explicit consideration for accurate prediction of fracture properties and the associated scatter. In this work, a hierarchical multi-scale approach is pursued to model microstructure sensitive brittle fracture. A quantitative phase-field based fracture model is utilized to capture the complex crack growth behavior in the microstructure and the related parameters are calibrated from lower length scale atomistic simulations instead of engineering scale experimental data. The workability of this approach is demonstrated by performing porosity dependent intergranular fracture simulations in UO 2 and comparingmore » the predictions with experiments.« less

Multi-scale modeling of microstructure dependent intergranular brittle fracture using a quantitative phase-field based method

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

Chakraborty, Pritam; Zhang, Yongfeng; Tonks, Michael R.

In this study, the fracture behavior of brittle materials is strongly influenced by their underlying microstructure that needs explicit consideration for accurate prediction of fracture properties and the associated scatter. In this work, a hierarchical multi-scale approach is pursued to model microstructure sensitive brittle fracture. A quantitative phase-field based fracture model is utilized to capture the complex crack growth behavior in the microstructure and the related parameters are calibrated from lower length scale atomistic simulations instead of engineering scale experimental data. The workability of this approach is demonstrated by performing porosity dependent intergranular fracture simulations in UO 2 and comparingmore » the predictions with experiments.« less

Simulation of Intergranular Ductile Cracking in β Titanium Alloys Based on a Micro-Mechanical Damage Model

PubMed Central

Li, Huan; Li, Jinshan; Tang, Bin; Fan, Jiangkun; Yuan, Huang

2017-01-01

The intergranular crack propagation of the lamellar structure β titanium alloys is investigated by using a modified Gurson-type damage model. The representative microstructure of the lamellar alloy, which consists of the soft α phase layer surrounding the hard grain interiors, is generated based on an advanced Voronoi algorithm. Both the normal fracture due to void growth and the shear fracture associated with void shearing are considered for the grain boundary α layer. The individual phase properties are determined according to the experimental nanoindentation result and the macroscopic stress–strain curve from a uni-axial tensile test. The effects of the strain hardening exponent of the grain interiors and the void shearing mechanism of the grain boundary α layer on fracture toughness and the intergranular crack growth behavior are emphatically studied. The computational predictions indicate that fracture toughness can be increased with increasing the strain hardening ability of the grain interiors and void shearing can be deleterious to fracture toughness. Based on the current simulation technique, qualitative understanding of relationships between the individual phase features and the fracture toughness of the lamellar alloys can be obtained, which provides useful suggestions to the heat treatment process of the β titanium alloys. PMID:29084171

Simulation of Intergranular Ductile Cracking in β Titanium Alloys Based on a Micro-Mechanical Damage Model.

PubMed

Li, Huan; Li, Jinshan; Tang, Bin; Fan, Jiangkun; Yuan, Huang

2017-10-30

The intergranular crack propagation of the lamellar structure β titanium alloys is investigated by using a modified Gurson-type damage model. The representative microstructure of the lamellar alloy, which consists of the soft α phase layer surrounding the hard grain interiors, is generated based on an advanced Voronoi algorithm. Both the normal fracture due to void growth and the shear fracture associated with void shearing are considered for the grain boundary α layer. The individual phase properties are determined according to the experimental nanoindentation result and the macroscopic stress-strain curve from a uni-axial tensile test. The effects of the strain hardening exponent of the grain interiors and the void shearing mechanism of the grain boundary α layer on fracture toughness and the intergranular crack growth behavior are emphatically studied. The computational predictions indicate that fracture toughness can be increased with increasing the strain hardening ability of the grain interiors and void shearing can be deleterious to fracture toughness. Based on the current simulation technique, qualitative understanding of relationships between the individual phase features and the fracture toughness of the lamellar alloys can be obtained, which provides useful suggestions to the heat treatment process of the β titanium alloys.

Double-sided laser beam welded T-joints for aluminum-lithium alloy aircraft fuselage panels: Effects of filler elements on microstructure and mechanical properties

NASA Astrophysics Data System (ADS)

Han, Bing; Tao, Wang; Chen, Yanbin; Li, Hao

2017-08-01

In the current work, T-joints consisting of 2.0 mm thick 2060-T8/2099-T83 aluminum-lithium alloys for aircraft fuselage panels have been fabricated by double-sided fiber laser beam welding with different filler wires. A new type wire CW3 (Al-6.2Cu-5.4Si) was studied and compared with conventional wire AA4047 (Al-12Si) mainly on microstructure and mechanical properties. It was found that the main combined function of Al-6.2%Cu-5.4%Si in CW3 resulted in considerable improvements especially on intergranular strength, hot cracking susceptibility and hoop tensile properties. Typical non-dendritic equiaxed zone (EQZ) was observed along welds' fusion boundary. Hot cracks and fractures during the load were always located within the EQZ, however, this typical zone could be restrained by CW3, effectively. Furthermore, changing of the main intergranular precipitated phase within the EQZ from T phase by AA4047 to T2 phase by CW3 also resulted in developments on microscopic intergranular reinforcement and macroscopic hoop tensile properties. In addition, bridging caused by richer substructure dendrites within CW3 weld's columnar zone resulted in much lower hot cracking susceptibility of the whole weld than AA4047.

Pressure-induced reversible amorphization and an amorphous-amorphous transition in Ge₂Sb₂Te₅ phase-change memory material.

PubMed

Sun, Zhimei; Zhou, Jian; Pan, Yuanchun; Song, Zhitang; Mao, Ho-Kwang; Ahuja, Rajeev

2011-06-28

Ge(2)Sb(2)Te(5) (GST) is a technologically very important phase-change material that is used in digital versatile disks-random access memory and is currently studied for the use in phase-change random access memory devices. This type of data storage is achieved by the fast reversible phase transition between amorphous and crystalline GST upon heat pulse. Here we report pressure-induced reversible crystalline-amorphous and polymorphic amorphous transitions in NaCl structured GST by ab initio molecular dynamics calculations. We have showed that the onset amorphization of GST starts at approximately 18 GPa and the system become completely random at approximately 22 GPa. This amorphous state has a cubic framework (c-amorphous) of sixfold coordinations. With further increasing pressure, the c-amorphous transforms to a high-density amorphous structure with trigonal framework (t-amorphous) and an average coordination number of eight. The pressure-induced amorphization is investigated to be due to large displacements of Te atoms for which weak Te-Te bonds exist or vacancies are nearby. Upon decompressing to ambient conditions, the original cubic crystalline structure is restored for c-amorphous, whereas t-amorphous transforms to another amorphous phase that is similar to the melt-quenched amorphous GST.

Pressure-induced transformations in amorphous silicon: A computational study

NASA Astrophysics Data System (ADS)

Garcez, K. M. S.; Antonelli, A.

2014-02-01

We study the transformations between amorphous phases of Si through molecular simulations using the environment dependent interatomic potential (EDIP) for Si. Our results show that upon pressure, the material undergoes a transformation from the low density amorphous (LDA) Si to the high density amorphous (HDA) Si. This transformation can be reversed by decompressing the material. This process, however, exhibits clear hysteresis, suggesting that the transformation LDA ↔ HDA is first-order like. The HDA phase is predominantly five-fold coordinated, whereas the LDA phase is the normal tetrahedrally bonded amorphous Si. The HDA phase at 400 K and 20 GPa was submitted to an isobaric annealing up to 800 K, resulting in a denser amorphous phase, which is structurally distinct from the HDA phase. Our results also show that the atomic volume and structure of this new amorphous phase are identical to those of the glass obtained by an isobaric quenching of the liquid in equilibrium at 2000 K and 20 GPa down to 400 K. The similarities between our results and those for amorphous ices suggest that this new phase is the very high density amorphous Si.

Pressure-induced reversible amorphization and an amorphous–amorphous transition in Ge2Sb2Te5 phase-change memory material

PubMed Central

Sun, Zhimei; Zhou, Jian; Pan, Yuanchun; Song, Zhitang; Mao, Ho-Kwang; Ahuja, Rajeev

2011-01-01

Ge2Sb2Te5 (GST) is a technologically very important phase-change material that is used in digital versatile disks-random access memory and is currently studied for the use in phase-change random access memory devices. This type of data storage is achieved by the fast reversible phase transition between amorphous and crystalline GST upon heat pulse. Here we report pressure-induced reversible crystalline-amorphous and polymorphic amorphous transitions in NaCl structured GST by ab initio molecular dynamics calculations. We have showed that the onset amorphization of GST starts at approximately 18 GPa and the system become completely random at approximately 22 GPa. This amorphous state has a cubic framework (c-amorphous) of sixfold coordinations. With further increasing pressure, the c-amorphous transforms to a high-density amorphous structure with trigonal framework (t-amorphous) and an average coordination number of eight. The pressure-induced amorphization is investigated to be due to large displacements of Te atoms for which weak Te–Te bonds exist or vacancies are nearby. Upon decompressing to ambient conditions, the original cubic crystalline structure is restored for c-amorphous, whereas t-amorphous transforms to another amorphous phase that is similar to the melt-quenched amorphous GST. PMID:21670255

Nature of phase transitions in crystalline and amorphous GeTe-Sb2Te3 phase change materials.

PubMed

Kalkan, B; Sen, S; Clark, S M

2011-09-28

The thermodynamic nature of phase stabilities and transformations are investigated in crystalline and amorphous Ge(1)Sb(2)Te(4) (GST124) phase change materials as a function of pressure and temperature using high-resolution synchrotron x-ray diffraction in a diamond anvil cell. The phase transformation sequences upon compression, for cubic and hexagonal GST124 phases are found to be: cubic → amorphous → orthorhombic → bcc and hexagonal → orthorhombic → bcc. The Clapeyron slopes for melting of the hexagonal and bcc phases are negative and positive, respectively, resulting in a pressure dependent minimum in the liquidus. When taken together, the phase equilibria relations are consistent with the presence of polyamorphism in this system with the as-deposited amorphous GST phase being the low entropy low-density amorphous phase and the laser melt-quenched and high-pressure amorphized GST being the high entropy high-density amorphous phase. The metastable phase boundary between these two polyamorphic phases is expected to have a negative Clapeyron slope. © 2011 American Institute of Physics

Multimillion atom simulations of dynamics of oxidation of an aluminum nanoparticle and nanoindentation on ceramics.

PubMed

Vashishta, Priya; Kalia, Rajiv K; Nakano, Aiichiro

2006-03-02

We have developed a first-principles-based hierarchical simulation framework, which seamlessly integrates (1) a quantum mechanical description based on the density functional theory (DFT), (2) multilevel molecular dynamics (MD) simulations based on a reactive force field (ReaxFF) that describes chemical reactions and polarization, a nonreactive force field that employs dynamic atomic charges, and an effective force field (EFF), and (3) an atomistically informed continuum model to reach macroscopic length scales. For scalable hierarchical simulations, we have developed parallel linear-scaling algorithms for (1) DFT calculation based on a divide-and-conquer algorithm on adaptive multigrids, (2) chemically reactive MD based on a fast ReaxFF (F-ReaxFF) algorithm, and (3) EFF-MD based on a space-time multiresolution MD (MRMD) algorithm. On 1920 Intel Itanium2 processors, we have demonstrated 1.4 million atom (0.12 trillion grid points) DFT, 0.56 billion atom F-ReaxFF, and 18.9 billion atom MRMD calculations, with parallel efficiency as high as 0.953. Through the use of these algorithms, multimillion atom MD simulations have been performed to study the oxidation of an aluminum nanoparticle. Structural and dynamic correlations in the oxide region are calculated as well as the evolution of charges, surface oxide thickness, diffusivities of atoms, and local stresses. In the microcanonical ensemble, the oxidizing reaction becomes explosive in both molecular and atomic oxygen environments, due to the enormous energy release associated with Al-O bonding. In the canonical ensemble, an amorphous oxide layer of a thickness of approximately 40 angstroms is formed after 466 ps, in good agreement with experiments. Simulations have been performed to study nanoindentation on crystalline, amorphous, and nanocrystalline silicon nitride and silicon carbide. Simulation on nanocrystalline silicon carbide reveals unusual deformation mechanisms in brittle nanophase materials, due to coexistence of brittle grains and soft amorphous-like grain boundary phases. Simulations predict a crossover from intergranular continuous deformation to intragrain discrete deformation at a critical indentation depth.

Structure and transport at grain boundaries in polycrystalline olivine: An atomic-scale perspective

NASA Astrophysics Data System (ADS)

Mantisi, Boris; Sator, Nicolas; Guillot, Bertrand

2017-12-01

Structure and transport properties at grain boundaries in polycrystalline olivine have been investigated at the atomic scale by molecular dynamics simulation (MD) using an empirical ionocovalent interaction potential. On the time scale of the simulation (a few tens of nanoseconds for a system size of ∼650,000 atoms) grain boundaries and grain interior were identified by mapping the atomic displacements along the simulation run. In the investigated temperature range (1300-1700 K) the mean thickness of the grain boundary phase is evaluated between 0.5 and 2 nm, a value which depends on temperature and grain size. The structure of the grain boundary phase is found to be disordered (amorphous-like) and is different from the one exhibited by the supercooled liquid. The self-diffusion coefficients of major elements in the intergranular region range from ∼10-13 to 10-10 m2/s between 1300 and 1700 K (with DSigb < DOgb < DFegb < DMggb) and are only one order of magnitude smaller than those evaluated in the supercooled melt. In using a newly derived expression for the bulk self-diffusion coefficient it is concluded that the latter one is driven by the grain boundary contribution as long as the grain size is smaller than a centimeter. In assuming that the electrical conduction at grain boundaries is purely ionic, the macroscopic grain boundary conductivity is found to be two orders of magnitude lower than in molten olivine, and one order of magnitude higher than the lattice conductivity. A consequence is that the conductivity of the olivine polycrystal is dominated by the grain interior contribution as soon as the grain size is larger than a micrometer or so. The grain boundary viscosity has been evaluated from the Green-Kubo relation expressing the viscosity as function of the stress tensor time correlation function. In spite of a slow convergence of the calculation by MD, the grain boundary viscosity was estimated about ∼105 Pa s at 1500 K, a value in agreement with high-temperature viscoelastic relaxation data. An interesting information gained from MD is that sliding at grain boundaries is essentially controlled by the internal friction between the intergranular phase and the grain edges.

Phase transformations during aging of a nitrogen-strengthened austenitic stainless steel

NASA Astrophysics Data System (ADS)

Ritter, Ann M.; Henry, Michael F.

1985-10-01

An analytical electron microscopy study was undertaken in order to characterize intergranular and matrix precipitation accompanying intermediate temperature aging in NITRONIC 50, a nitrogen-strengthened austenitic stainless steel. Extensive precipitation on most grain boundaries had occurred after aging for 24 hours at 675 °C. The primary intergranular phase at that time was Cr-rich M23C6, and energy dispersive spectra taken on grain boundary segments between these carbides indicated Cr-depletion and Fe- and Ni-enhancement relative to the matrix. After aging for 336 and 1008 hours at 675 °C, M6C (eta-carbide) precipitates were also present on grain boundaries. These precipitates were distinguished from M23C6 on the basis of their lattice parameters and chemistries, with M6C containing less Cr and Fe, and more Ni, Mo, and Si than M23C6. The differences in chemistry were clarified by a statistical treatment of the spectra. The statistical analysis also showed that precipitates with a range of chemistries between M23C6 and M6C coexisted with these phases on the grain boundaries. Associated with this shift in precipitate stoichiometry was an increase in the average concentration of Cr and a decrease in the average concentration of Ni at the grain boundaries. Intergranular sigma phase was also observed after times 24 hours at 675 °C, with sigma precipitating on grain boundaries containing carbides. Intragranular precipitates observed to be stable up to 1008 hours at 675 °C included Z-phase, a complex nitride which had formed during solution annealing; M7C3 carbides, which nucleated at Z-phase/austenite interfaces; M23C6 carbides, which precipitated on incoherent twin boundaries; and Cr-rich MN precipitates, which nucleated on dislocations.

Phase change in CoTi2 induced by MeV electron irradiation

NASA Astrophysics Data System (ADS)

Zensho, Akihiro; Sato, Kazuhisa; Yasuda, Hidehiro; Mori, Hirotaro

2018-07-01

The phase change induced by MeV electron irradiation in the intermetallic compound E93-CoTi2 was investigated using high-voltage electron microscopy. Under MeV electron irradiation, CoTi2 was first transformed into an amorphous phase and, with continued irradiation, crystallite formation in the amorphous phase (i.e. formation of crystallites of a solid-solution phase within the amorphous phase) was induced. The critical temperature for amorphisation was around 250 K. The total dose (dpa) required for crystallite formation (i.e. that required for partial crystallisation) was high (i.e. 27-80 dpa) and, even after prolonged irradiation, the amorphous phase was retained in the irradiated sample. Such partial crystallisation behaviour of amorphous Co33Ti67 was clearly different from the crystallisation behaviour (i.e. amorphous-to-solid solution, polymorphous transformation) of amorphous Cr67Ti33 reported in the literature. A possible cause of the difference is discussed.

Amorphous-amorphous transition in a porous coordination polymer.

PubMed

Ohtsu, Hiroyoshi; Bennett, Thomas D; Kojima, Tatsuhiro; Keen, David A; Niwa, Yasuhiro; Kawano, Masaki

2017-07-04

The amorphous state plays a key role in porous coordination polymer and metal-organic framework phase transitions. We investigate a crystalline-to-amorphous-to-amorphous-to-crystalline (CAAC) phase transition in a Zn based coordination polymer, by X-ray absorption fine structure (XAFS) and X-ray pair distribution function (PDF) analysis. We show that the system shows two distinct amorphous phases upon heating. The first involves a reversible transition to a desolvated form of the original network, followed by an irreversible transition to an intermediate phase which has elongated Zn-I bonds.

Self-organization of a periodic structure between amorphous and crystalline phases in a GeTe thin film induced by femtosecond laser pulse amorphization

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

Katsumata, Y.; Morita, T.; Morimoto, Y.

A self-organized fringe pattern in a single amorphous mark of a GeTe thin film was formed by multiple femtosecond pulse amorphization. Micro Raman measurement indicates that the fringe is a periodic alternation between crystalline and amorphous phases. The period of the fringe is smaller than the irradiation wavelength and the direction is parallel to the polarization direction. Snapshot observation revealed that the fringe pattern manifests itself via a complex but coherent process, which is attributed to crystallization properties unique to a nonthermally amorphized phase and the distinct optical contrast between crystalline and amorphous phases.

Theory of amorphous ices.

PubMed

Limmer, David T; Chandler, David

2014-07-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens.

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics

PubMed Central

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-01-01

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics. PMID:25297473

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics.

PubMed

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-10-09

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics.

Theory of amorphous ices

PubMed Central

Limmer, David T.; Chandler, David

2014-01-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens. PMID:24858957

Phase transformations in amorphous fullerite C60 under high pressure and high temperature

NASA Astrophysics Data System (ADS)

Borisova, P. A.; Blanter, M. S.; Brazhkin, V. V.; Somenkov, V. A.; Filonenko, V. P.

2015-08-01

First phase transformations of amorphous fullerite C60 at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С60 molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature-pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.

Intergranular metal phase increases thermal shock resistance of ceramic coating

NASA Technical Reports Server (NTRS)

Carpenter, H. W.

1966-01-01

Dispersed copper phase increases the thermal shock resistance of a plasma-arc-sprayed coating of zirconia used as a heat barrier on a metal substrate. A small amount of copper is deposited on the granules of the zirconia powder before arc-spraying the resultant powder composite onto the substrate.

Effects of Intergranular Gas Bubbles on Thermal Conductivity

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

K. Chockalingam; Paul C. Millett; M. R. Tonks

2012-11-01

Model microstructures obtained from phase-field simulations are used to study the effective heat transfer across bicrys- tals with stationary grain boundary bubble populations. We find that the grain boundary coverage, irrespective of the intergranular bubble radii, is the most relevant parameter to the thermal resistance, which we use to derive effec- tive Kapitza resistances that are dependent on the grain boundary coverage and Kaptiza resistance of the intact grain boundary. We propose a model to predict thermal conductivity as a function of porosity, grain-size, Kaptiza resistance of the intact grain boundary, and grain boundary bubble coverage.

The composition of secondary amorphous phases under different environmental conditions

NASA Astrophysics Data System (ADS)

Smith, R.; Rampe, E. B.; Horgan, B. H. N.; Dehouck, E.; Morris, R. V.

2017-12-01

X-ray diffraction (XRD) patterns measured by the CheMin instrument on the Mars Science Laboratory Curiosity rover demonstrate that amorphous phases are major components ( 15-60 wt%) of all rock and soil samples in Gale Crater. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., silica, ferrihydrite) phases. Secondary amorphous phases are frequently found as weathering products in soils on Earth, but these materials remain poorly characterized. Here we study a diverse suite of terrestrial samples including: sediments from recently de-glaciated volcanoes (Oregon), modern volcanic soils (Hawaii), and volcanic paleosols (Oregon) in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of amorphous phases. We combine bulk XRD mineralogy with bulk chemical compositions (XRF) to calculate the abundance and bulk composition of the amorphous materials in our samples. We then utilize scanning transmission electron microscopy (STEM) and energy dispersive x-ray spectroscopy (EDS) to study the composition of individual amorphous phases at the micrometer scale. XRD analyses of 8 samples thus far indicate that the abundance of amorphous phases are: modern soils (20-80 %) > paleosols (15-40 %) > glacial samples (15-30 %). Initial calculations suggest that the amorphous components consist primarily of SiO2, Al2O3, TiO2, FeO and Fe2O3, with minor amounts of other oxides (e.g., MgO, CaO, Na2O). Compared to their respective crystalline counterparts, calculations indicate bulk amorphous components enriched in SiO2 for the glacial sample, and depleted in SiO2 for the modern soil and paleosol samples. STEM analyses reveal that the amorphous components consist of a number of different phases. Of the two samples analyzed using STEM thus far, the secondary amorphous phases have compositions with varying ratios of SiO2, Al2O3, TiO2, and Fe-oxides, consistent with mass balance calculation results, but inconsistent with well-known amorphous phase compositions (e.g., allophane, ferrihydrite). These results show that a number of secondary amorphous phases can form within a single soil environment. Continued analysis can help determine whether compositional trends can be linked to environmental factors.

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.

Study of the solid-state amorphization of (GaSb){sub 1-x}Ge{sub x} semiconductors by real-time neutron diffraction and electron microscopy

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

Fedotov, V. K., E-mail: fedotov@issp.ac.ru; Ponyatovsky, E. G.

2011-12-15

The spontaneous amorphization of high-pressure quenched phases of the GaSb-Ge system has been studied by neutron diffraction while slowly heating the phases at atmospheric pressure. The sequence of changes in the structural parameters of the initial crystalline phase and the final amorphous phase is established. The behavior of the phases and the correlation in the structural features of the phase transitions and anomalous thermal effects exhibit signs of the inhomogeneous model of solid-state amorphization.

Influences of semiconductor morphology on the mechanical fatigue behavior of flexible organic electronics

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

Lee, Young-Joo; Yeon, Han-Wool; Shin, Hae-A-Seul

2013-12-09

The influence of crystalline morphology on the mechanical fatigue of organic semiconductors (OSCs) was investigated using 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) as a crystalline OSC and poly(triarylamine) (PTAA) as an amorphous OSC. During cyclic bending, resistances of the OSCs were monitored using the transmission-line method on a metal-semiconductor-metal structure. The resistance of the TIPS-pentacene increased under fatigue damage in tensile-stress mode, but no such degradation was observed in the PTAA. Both OSCs were stable under compressive bending fatigue. The formation of intergranular cracks at the domain boundaries of the TIPS-pentacene was responsible for the degradation of its electrical properties under tensile bending fatigue.

Microstructure Evolution and Related Magnetic Properties of Cu-Zr-Al-Gd Phase-Separating Metallic Glasses

NASA Astrophysics Data System (ADS)

Kim, Sang Jun; Kim, Jinwoo; Park, Eun Soo

2018-04-01

We carefully investigated the correlation between microstructures and magnetic properties of Cu-Zr-Al-Gd phase-separating metallic glasses (PSMGs). The saturation magnetizations of the PSMGs were determined by total Gd contents of the alloys, while their coercivity exhibits a large deviation by the occurrence of phase separation due to the boundary pinning effect of hierarchically separated amorphous phases. Especially, the PSMGs containing Gd-rich amorphous nanoparticles show the highest coercivity which can be attributed to the size effect of the ferromagnetic amorphous phase. Furthermore, the selective crystallization of ferromagnetic amorphous phases can affect the magnetization behavior of the PSMGs. Our results could provide a novel strategy for tailoring unique soft magnetic properties of metallic glasses by introducing hierarchically separated amorphous phases and controlling their crystallinity.

Microstructure Evolution and Related Magnetic Properties of Cu-Zr-Al-Gd Phase-Separating Metallic Glasses

NASA Astrophysics Data System (ADS)

Kim, Sang Jun; Kim, Jinwoo; Park, Eun Soo

2018-06-01

We carefully investigated the correlation between microstructures and magnetic properties of Cu-Zr-Al-Gd phase-separating metallic glasses (PSMGs). The saturation magnetizations of the PSMGs were determined by total Gd contents of the alloys, while their coercivity exhibits a large deviation by the occurrence of phase separation due to the boundary pinning effect of hierarchically separated amorphous phases. Especially, the PSMGs containing Gd-rich amorphous nanoparticles show the highest coercivity which can be attributed to the size effect of the ferromagnetic amorphous phase. Furthermore, the selective crystallization of ferromagnetic amorphous phases can affect the magnetization behavior of the PSMGs. Our results could provide a novel strategy for tailoring unique soft magnetic properties of metallic glasses by introducing hierarchically separated amorphous phases and controlling their crystallinity.

In situ observation of shear-driven amorphization in silicon crystals.

PubMed

He, Yang; Zhong, Li; Fan, Feifei; Wang, Chongmin; Zhu, Ting; Mao, Scott X

2016-10-01

Amorphous materials are used for both structural and functional applications. An amorphous solid usually forms under driven conditions such as melt quenching, irradiation, shock loading or severe mechanical deformation. Such extreme conditions impose significant challenges on the direct observation of the amorphization process. Various experimental techniques have been used to detect how the amorphous phases form, including synchrotron X-ray diffraction, transmission electron microscopy (TEM) and Raman spectroscopy, but a dynamic, atomistic characterization has remained elusive. Here, by using in situ high-resolution TEM (HRTEM), we show the dynamic amorphization process in silicon nanocrystals during mechanical straining on the atomic scale. We find that shear-driven amorphization occurs in a dominant shear band starting with the diamond-cubic (dc) to diamond-hexagonal (dh) phase transition and then proceeds by dislocation nucleation and accumulation in the newly formed dh-Si phase. This process leads to the formation of an amorphous Si (a-Si) band, embedded with dh-Si nanodomains. The amorphization of dc-Si via an intermediate dh-Si phase is a previously unknown pathway of solid-state amorphization.

SedFoam-2.0: a 3-D two-phase flow numerical model for sediment transport

NASA Astrophysics Data System (ADS)

Chauchat, Julien; Cheng, Zhen; Nagel, Tim; Bonamy, Cyrille; Hsu, Tian-Jian

2017-11-01

In this paper, a three-dimensional two-phase flow solver, SedFoam-2.0, is presented for sediment transport applications. The solver is extended from twoPhaseEulerFoam available in the 2.1.0 release of the open-source CFD (computational fluid dynamics) toolbox OpenFOAM. In this approach the sediment phase is modeled as a continuum, and constitutive laws have to be prescribed for the sediment stresses. In the proposed solver, two different intergranular stress models are implemented: the kinetic theory of granular flows and the dense granular flow rheology μ(I). For the fluid stress, laminar or turbulent flow regimes can be simulated and three different turbulence models are available for sediment transport: a simple mixing length model (one-dimensional configuration only), a k - ɛ, and a k - ω model. The numerical implementation is demonstrated on four test cases: sedimentation of suspended particles, laminar bed load, sheet flow, and scour at an apron. These test cases illustrate the capabilities of SedFoam-2.0 to deal with complex turbulent sediment transport problems with different combinations of intergranular stress and turbulence models.

Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule.

PubMed

Politi, Yael; Metzler, Rebecca A; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P U P A; Gilbert, Pupa

2008-11-11

Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40-200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism.

Amorphous Phases on the Surface of Mars

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Morris, R. V.; Ruff, S. W.; Horgan, B.; Dehouck, E.; Achilles, C. N.; Ming, D. W.; Bish, D. L.; Chipera, S. J.

2014-01-01

Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made up of mixed phases (e.g., palagonite) and synthetic single phases to determine their short-range order structures and calculate their XRD patterns to use in models of CheMin data. Finally, to address the timing of the alteration, we need to study rocks on the martian surface of different ages that may contain glass (volcanic or impact) with MSL and future rovers to better understand how glass alters on the martian surface, if that alteration mechanism is universal, and if alteration spans across long periods of time or if there is a time past which unaltered glass remains.

Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions.

PubMed

Shibata, Naoya; Pennycook, Stephen J; Gosnell, Tim R; Painter, Gayle S; Shelton, William A; Becher, Paul F

2004-04-15

Silicon nitride (Si3N4) ceramics are used in numerous applications because of their superior mechanical properties. Their intrinsically brittle nature is a critical issue, but can be overcome by introducing whisker-like microstructural features. However, the formation of such anisotropic grains is very sensitive to the type of cations used as the sintering additives. Understanding the origin of dopant effects, central to the design of high-performance Si3N4 ceramics, has been sought for many years. Here we show direct images of dopant atoms (La) within the nanometre-scale intergranular amorphous films typically found at grain boundaries, using aberration corrected Z-contrast scanning transmission electron microscopy. It is clearly shown that the La atoms preferentially segregate to the amorphous/crystal interfaces. First-principles calculations confirm the strong preference of La for the crystalline surfaces, which is essential for forming elongated grains and a toughened microstructure. Whereas principles of micrometre-scale structural design are currently used to improve the mechanical properties of ceramics, this work represents a step towards the atomic-level structural engineering required for the next generation of ceramics.

Possible Existence of Two Amorphous Phases of D-Mannitol Related by a First-Order Transition

NASA Astrophysics Data System (ADS)

Zhu, Men; Wang, Jun-Qiang; Perepezko, John; Yu, Lian

We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above Tg (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase (Phase X). The enthalpy of Phase X is roughly halfway between those of the known amorphous and crystalline phases. The amorphous nature of Phase X is suggested by its absence of birefringence, transparency, broad X-ray diffraction, and broad Raman and NIR spectra. Phase X has greater molecular spacing, higher molecular order, fewer intra- and more inter-molecular hydrogen bonds than the normal liquid. On fast heating, Phase X transforms back to SCL near 330 K. Upon temperature cycling, it shows a glass-transition-like change of heat capacity. The presence of D-sorbitol enables a first-order liquid-liquid transition (LLT) from SCL to Phase X. This is the first report of polyamorphism at 1 atm for a pharmaceutical relevant substance. As amorphous solids are explored for many applications, polyamorphism could offer a tool to engineer the properties of materials. (Ref: M. Zhu et al., J. Chem. Phys. 2015, 142, 244504)

X-Ray Amorphous Phases in Terrestrial Analog Volcanic Sediments: Implications for Amorphous Phases in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Smith, R. J.; Horgan, B.; Rampe, E.; Dehouck, E.; Morris, R. V.

2017-01-01

X-ray diffraction (XRD) amorphous phases have been found as major components (approx.15-60 wt%) of all rock and soil samples measured by the CheMin XRD instrument in Gale Crater, Mars. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., allophane) phases. Amorphous phases form in abundance during surface weathering on Earth. Yet, these materials are poorly characterized, and it is not certain how properties like composition and structure change with formation environment. The presence of poorly crystalline phases can be inferred from XRD patterns by the appearance of a low angle rise (< or approx.10deg 2(theta)) or broad peaks in the background at low to moderate 2(theta) angles (amorphous humps). CheMin mineral abundances combined with bulk chemical composition measurements from the Alpha Particle X-ray Spectrometer (APXS) have been used to estimate the abundance and composition of the XRD amorphous materials in soil and rock samples on Mars. Here we apply a similar approach to a diverse suite of terrestrial samples - modern soils, glacial sediments, and paleosols - in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of X-ray amorphous phases.

Kinetically Controlled Two-Step Amorphization and Amorphous-Amorphous Transition in Ice.

PubMed

Lin, Chuanlong; Yong, Xue; Tse, John S; Smith, Jesse S; Sinogeikin, Stanislav V; Kenney-Benson, Curtis; Shen, Guoyin

2017-09-29

We report the results of in situ structural characterization of the amorphization of crystalline ice Ih under compression and the relaxation of high-density amorphous (HDA) ice under decompression at temperatures between 96 and 160 K by synchrotron x-ray diffraction. The results show that ice Ih transforms to an intermediate crystalline phase at 100 K prior to complete amorphization, which is supported by molecular dynamics calculations. The phase transition pathways show clear temperature dependence: direct amorphization without an intermediate phase is observed at 133 K, while at 145 K a direct Ih-to-IX transformation is observed; decompression of HDA shows a transition to low-density amorphous ice at 96 K and ∼1  Pa, to ice Ic at 135 K and to ice IX at 145 K. These observations show that the amorphization of compressed ice Ih and the recrystallization of decompressed HDA are strongly dependent on temperature and controlled by kinetic barriers. Pressure-induced amorphous ice is an intermediate state in the phase transition from the connected H-bond water network in low pressure ices to the independent and interpenetrating H-bond network of high-pressure ices.

Kinetically Controlled Two-Step Amorphization and Amorphous-Amorphous Transition in Ice

NASA Astrophysics Data System (ADS)

Lin, Chuanlong; Yong, Xue; Tse, John S.; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kenney-Benson, Curtis; Shen, Guoyin

2017-09-01

We report the results of in situ structural characterization of the amorphization of crystalline ice Ih under compression and the relaxation of high-density amorphous (HDA) ice under decompression at temperatures between 96 and 160 K by synchrotron x-ray diffraction. The results show that ice Ih transforms to an intermediate crystalline phase at 100 K prior to complete amorphization, which is supported by molecular dynamics calculations. The phase transition pathways show clear temperature dependence: direct amorphization without an intermediate phase is observed at 133 K, while at 145 K a direct Ih-to-IX transformation is observed; decompression of HDA shows a transition to low-density amorphous ice at 96 K and ˜1 Pa , to ice Ic at 135 K and to ice IX at 145 K. These observations show that the amorphization of compressed ice Ih and the recrystallization of decompressed HDA are strongly dependent on temperature and controlled by kinetic barriers. Pressure-induced amorphous ice is an intermediate state in the phase transition from the connected H-bond water network in low pressure ices to the independent and interpenetrating H-bond network of high-pressure ices.

Kinetically Controlled Two-Step Amorphization and Amorphous-Amorphous Transition in Ice

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

Lin, Chuanlong; Yong, Xue; Tse, John S.

We report the results of in situ structural characterization of the amorphization of crystalline ice Ih under compression and the relaxation of high-density amorphous (HDA) ice under decompression at temperatures between 96 and 160 K by synchrotron x-ray diffraction. The results show that ice Ih transforms to an intermediate crystalline phase at 100 K prior to complete amorphization, which is supported by molecular dynamics calculations. The phase transition pathways show clear temperature dependence: direct amorphization without an intermediate phase is observed at 133 K, while at 145 K a direct Ih-to-IX transformation is observed; decompression of HDA shows a transitionmore » to low-density amorphous ice at 96 K and ~ 1 Pa , to ice Ic at 135 K and to ice IX at 145 K. These observations show that the amorphization of compressed ice Ih and the recrystallization of decompressed HDA are strongly dependent on temperature and controlled by kinetic barriers. Pressure-induced amorphous ice is an intermediate state in the phase transition from the connected H-bond water network in low pressure ices to the independent and interpenetrating H-bond network of high-pressure ices.« less

Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule

PubMed Central

Politi, Yael; Metzler, Rebecca A.; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H.; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P. U. P. A.

2008-01-01

Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism. PMID:18987314

Mechanisms of devitrification of grain boundary glassy phases in Si3N4 materials

NASA Technical Reports Server (NTRS)

Hench, L. L.

1982-01-01

Changes in the grain boundary (g.b.) phases of Si3N4 are analyzed, the effects of composition and thermal history on devitrification of the g.b. phases are determined, devitrification of the g.b. phases of Si3N are related to mechanical behavior and oxidation sensitivity of the material. The phase relationships that occur within the grain boundaries of Si3N4 containing various densification aids are reviewed. Comparisons of the effects of MgO, Y2O3, CeO2, and Y2O3 + AL2O3 are made in terms of the phase equilibria of the Si3N4 + SiO2 + additive compositional system. Two new equilibrium phase diagrams for the Si3N4-SiO2 and Y2O3 and Si3N4-SiO2-Ce2O3 systems are preented. The effects of Y2O3 vs CeO2 densification aids on the fracture surfaces of Si3N4 are compared. Auger electron spectroscopy shows that both oxides are concentrated within the fracture surface. Scanning electron microscopy shows evidence that Si3N4 with CeO2 formed an intergranular structure of fine grained oxynitride reaction products, as predicted by phase quilibria, whereas the Y2O3 containing sample shows evidence of an intergranular glassy phase.

Amorphous Phase Characterization Through X-Ray Diffraction Profile Modeling: Implications for Amorphous Phases in Gale Crater Rocks and Soils

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Downs, G. W.; Downs, R. T.; Morris, R. V.; Rampe, E. B.; Ming, D. W.; Chipera, S. J.; Blake, D. F.; Vaniman, D. T.; Bristow, T. F.;

Nature of metastable amorphous-to-crystalline reversible phase transformations in GaSb

NASA Astrophysics Data System (ADS)

Kalkan, B.; Edwards, T. G.; Raoux, S.; Sen, S.

2013-08-01

The structural, thermodynamic, and kinetic aspects of the transformations between the metastable amorphous and crystalline phases of GaSb are investigated as a function of pressure at ambient temperature using synchrotron x-ray diffraction experiments in a diamond anvil cell. The results are consistent with the hypothesis that the pressure induced crystallization of amorphous GaSb into the β-Sn crystal structure near ˜5 GPa is possibly a manifestation of an underlying polyamorphic phase transition between a semiconducting, low density and a metallic, high density amorphous (LDA and HDA, respectively) phases. In this scenario, the large differences in the thermal crystallization kinetics between amorphous GaSb deposited in thin film form by sputtering and that prepared by laser melt quenching may be related to the relative location of the glass transition temperature of the latter in the pressure-temperature (P-T) space with respect to the location of the critical point that terminate the LDA ↔ HDA transition. The amorphous → β-Sn phase transition is found to be hysteretically reversible as the β-Sn phase undergoes decompressive amorphization near ˜2 GPa due to the lattice instabilities that give rise to density fluctuations in the crystal upon decompression.

Processing and characterization of Zr-based metallic glass by laser direct deposition

NASA Astrophysics Data System (ADS)

Bae, Heehun

Bulk Metallic Glass has become famous for its exceptional mechanical and corrosion properties. Especially, Zirconium has been the prominent constituent in Bulk Metallic Glass due to its superior glass forming ability, the ability to form amorphous phase with low cooling rate, thereby giving advantages in structural applications. In this study, Zirconium powder was alloyed with Aluminum, Nickel and Copper powder at an atomic ratio of 65:10:10:15, respectively. Using the ball milling process to mix the powders, Zr65Al10Ni 10Cu15 amorphous structure was manufactured by laser direct deposition. Laser power and laser scanning speed were optimized to increase the fraction of amorphous phase. X-ray Diffraction confirmed the existence of both amorphous and crystalline phase by having a wide halo peak and sharp intense peak in the spectrum. Differential Scanning Calorimetry proved the presence of amorphous phase and glass transition was observed to be around 655 K. Scanning electron microscopy showed the microstructure of the deposited sample to have repetitive amorphous and crystalline phase as XRD examined. Crystalline phase resulted from the laser reheating and remelting process due to subsequent laser scan. Laser direct deposited amorphous/crystalline composite showed Vickers Hardness of 670 Hv and exhibited improved corrosion resistance in comparison to fully-crystallized sample. The compression test showed that, due to the existence of crystalline phase, fracture strain of Zr65Al10Ni10Cu 15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass.

Toughening Fe-based Amorphous Coatings by Reinforcement of Amorphous Carbon.

PubMed

Wang, Wei; Zhang, Cheng; Zhang, Zhi-Wei; Li, Yi-Cheng; Yasir, Muhammad; Wang, Hai-Tao; Liu, Lin

2017-06-22

Toughening of Fe-based amorphous coatings meanwhile maintaining a good corrosion resistance remains challenging. This work reports a novel approach to improve the toughness of a FeCrMoCBY amorphous coating through in-situ formation of amorphous carbon reinforcement without reducing the corrosion resistance. The Fe-based composite coating was prepared by high velocity oxy-fuel (HVOF) thermal spraying using a pre-mixed Fe-based amorphous/nylon-11 polymer feedstock powders. The nylon-11 powders were in-situ carbonized to amorphous carbon phase during thermal spraying process, which homogeneously distributed in the amorphous matrix leading to significant enhancement of toughness of the coating. The mechanical properties, including hardness, impact resistance, bending and fatigue strength, were extensively studied by using a series of mechanical testing techniques. The results revealed that the composite coating reinforced by amorphous carbon phase exhibited enhanced impact resistance and nearly twice-higher fatigue strength than that of the monolithic amorphous coating. The enhancement of impact toughness and fatigue properties is owed to the dumping effect of the soft amorphous carbon phase, which alleviated stress concentration and decreased crack propagation driving force.

Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

PubMed

Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

2017-09-01

The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium phosphate (ACP) environments could also arise from a transient amorphous precursor phase of apatite. Here, we provide an NMR spectroscopy methodology to reveal the origin of these ACP environments in bone mineral or in biomimetic apatite. The 1 H magnetization exchange between protons arising from amorphous and crystalline domains shows unambiguously that an ACP layer coats the apatitic crystalline core of bone et biomimetic apatite platelets. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Magnetotransport properties of microstructured AlCu2Mn Heusler alloy thin films in the amorphous and crystalline phase

NASA Astrophysics Data System (ADS)

Barzola-Quiquia, José; Stiller, Markus; Esquinazi, Pablo D.; Quispe-Marcatoma, Justiniano; Häussler, Peter

2018-06-01

We have studied the resistance, magnetoresistance and Hall effect of AlCu2Mn Heusler alloy thin films prepared by flash evaporation on substrates cooled at 4He liquid temperature. The as-prepared samples were amorphous and were annealed stepwise to induce the transformation to the crystalline phase. The amorphous phase is metastable up to above room temperature and the transition to the crystalline phase was observed by means of resistance measurements. Using transmission electron microscopy, we have determined the structure factor S (K) and the pair correlation function g (r) , both results indicate that amorphous AlCu2Mn is an electronic stabilized phase. The X-ray diffraction of the crystallized film shows peaks corresponding to the well ordered L21 phase. The resistance shows a negative temperature coefficient in both phases. The magnetoresistance (MR) is negative in both phases, yet larger in the crystalline state compared to the amorphous one. The magnetic properties were studied further by anomalous Hall effect measurements, which were present in both phases. In the amorphous state, the anomalous Hall effect disappears at temperatures below 175 K and is present up to above room temperature in the case of crystalline AlCu2Mn.

Key experimental information on intermediate-range atomic structures in amorphous Ge2Sb2Te5 phase change material

NASA Astrophysics Data System (ADS)

Hosokawa, Shinya; Pilgrim, Wolf-Christian; Höhle, Astrid; Szubrin, Daniel; Boudet, Nathalie; Bérar, Jean-François; Maruyama, Kenji

2012-04-01

Laser-induced crystalline-amorphous phase change of Ge-Sb-Te alloys is the key mechanism enabling the fast and stable writing/erasing processes in rewritable optical storage devices, such as digital versatile disk (DVD) or blu-ray disk. Although the structural information in the amorphous phase is essential for clarifying this fast process, as well as long lasting stabilities of both the phases, experimental works were mostly limited to the short-range order by x ray absorption fine structure. Here we show both the short and intermediate-range atomic structures of amorphous DVD material, Ge2Sb2Te5 (GST), investigated by a combination of anomalous x ray scattering and reverse Monte Carlo modeling. From the obtained atomic configurations of amorphous GST, we have found that the Sb atoms and half of the Ge atoms play roles in the fast phase change process of order-disorder transition, while the remaining Ge atoms act for the proper activation energy of barriers between the amorphous and crystalline phases.

Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III

1991-01-01

The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

Effects of temperature dependent pre-amorphization implantation on NiPt silicide formation and thermal stability on Si(100)

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

Ozcan, Ahmet S.; Wall, Donald; Jordan-Sweet, Jean

Using temperature controlled Si and C ion implantation, we studied the effects of pre-amorphization implantation on NiPt alloy silicide phase formation. In situ synchrotron x-ray diffraction and resistance measurements were used to monitor phase and morphology evolution in silicide films. Results show that substrate amorphization strongly modulate the nucleation of silicide phases, regardless of implant species. However, morphological stability of the thin films is mainly enhanced by C addition, independently of the amorphization depth.

Ion migration in crystalline and amorphous HfOX

NASA Astrophysics Data System (ADS)

Schie, Marcel; Müller, Michael P.; Salinga, Martin; Waser, Rainer; De Souza, Roger A.

2017-03-01

The migration of ions in HfOx was investigated by means of large-scale, classical molecular-dynamics simulations over the temperature range 1000 ≤T /K ≤2000 . Amorphous HfOx was studied in both stoichiometric and oxygen-deficient forms (i.e., with x = 2 and x = 1.9875); oxygen-deficient cubic and monoclinic phases were also studied. The mean square displacement of oxygen ions was found to evolve linearly as a function of time for the crystalline phases, as expected, but displayed significant negative deviations from linear behavior for the amorphous phases, that is, the behavior was sub-diffusive. That oxygen-ion migration was observed for the stoichiometric amorphous phase argues strongly against applying the traditional model of vacancy-mediated migration in crystals to amorphous HfO2. In addition, cation migration, whilst not observed for the crystalline phases (as no cation defects were present), was observed for both amorphous phases. In order to obtain activation enthalpies of migration, the residence times of the migrating ions were analyzed. The analysis reveals four activation enthalpies for the two amorphous phases: 0.29 eV, 0.46 eV, and 0.66 eV (values very close to those obtained for the monoclinic structure) plus a higher enthalpy of at least 0.85 eV. In comparison, the cubic phase is characterized by a single value of 0.43 eV. Simple kinetic Monte Carlo simulations suggest that the sub-diffusive behavior arises from nanoscale confinement of the migrating ions.

A compressible two-phase model for dispersed particle flows with application from dense to dilute regimes

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

McGrath, Thomas P., E-mail: thomas.p.mcgrath@navy.mil; St Clair, Jeffrey G.; Department of Mechanical and Aerospace Engineering, University of Florida, 231 MAE-A, P.O. Box 116250, Gainesville, Florida 32611

2016-05-07

Multiphase flows are present in many important fields ranging from multiphase explosions to chemical processing. An important subset of multiphase flow applications involves dispersed materials, such as particles, droplets, and bubbles. This work presents an Eulerian–Eulerian model for multiphase flows containing dispersed particles surrounded by a continuous media such as air or water. Following a large body of multiphase literature, the driving force for particle acceleration is modeled as a direct function of both the continuous-phase pressure gradient and the gradient of intergranular stress existing within the particle phase. While the application of these two components of driving force ismore » well accepted in much of the literature, other models exist in which the particle-phase pressure gradient itself drives particle motion. The multiphase model treats all phases as compressible and is derived to ensure adherence to the 2nd Law of Thermodynamics. The governing equations are presented and discussed, and a characteristic analysis shows the model to be hyperbolic, with a degeneracy in the case that the intergranular stress, which is modeled as a configuration pressure, is zero. Finally, results from a two sample problems involving shock-induced particle dispersion are presented. The results agree well with experimental measurements, providing initial confidence in the proposed model.« less

Three-dimensional nanomechanical mapping of amorphous and crystalline phase transitions in phase-change materials.

PubMed

Grishin, Ilja; Huey, Bryan D; Kolosov, Oleg V

2013-11-13

The nanostructure of micrometer-sized domains (bits) in phase-change materials (PCM) that undergo switching between amorphous and crystalline phases plays a key role in the performance of optical PCM-based memories. Here, we explore the dynamics of such phase transitions by mapping PCM nanostructures in three dimensions with nanoscale resolution by combining precision Ar ion beam cross-sectional polishing and nanomechanical ultrasonic force microscopy (UFM) mapping. Surface and bulk phase changes of laser written submicrometer to micrometer sized amorphous-to-crystalline (SET) and crystalline-to-amorphous (RESET) bits in chalcogenide Ge2Sb2Te5 PCM are observed with 10-20 nm lateral and 4 nm depth resolution. UFM mapping shows that the Young's moduli of crystalline SET bits exceed the moduli of amorphous areas by 11 ± 2%, with crystalline content extending from a few nanometers to 50 nm in depth depending on the energy of the switching pulses. The RESET bits written with 50 ps pulses reveal shallower depth penetration and show 30-50 nm lateral and few nanometer vertical wavelike topography that is anticorrelated with the elastic modulus distribution. Reverse switching of amorphous RESET bits results in the full recovery of subsurface nanomechanical properties accompanied with only partial topography recovery, resulting in surface corrugations attributed to quenching. This precision sectioning and nanomechanical mapping approach could be applicable to a wide range of amorphous, nanocrystalline, and glass-forming materials for 3D nanomechanical mapping of amorphous-crystalline transitions.

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

Makino, Nobuaki; Toshiba Corporation, 33 Shin-Isogo-Cho, Isogo-ku, Yokohama 235-0017; Shigeta, Yukichi

The stabilization of the amorphous structure in amorphous silicon film by adding Ge atoms was studied using Raman spectroscopy. Amorphous Si{sub 1−x}Ge{sub x} (x = 0.0, 0.03, 0.14, and 0.27) films were deposited on glass substrates from electron beam evaporation sources and annealed in N{sub 2} atmosphere. The change in the amorphous states and the phase transition from amorphous to crystalline were characterized using the TO, LO, and LA phonons in the Raman spectra. The temperature of the transition from the amorphous phase to the crystalline phase was higher for the a-Si{sub 1−x}Ge{sub x} (x = 0.03, 0.14) films, and the crystallization was hindered.more » The reason why the addition of a suitable quantity of Ge atoms into the three-dimensional amorphous silicon network stabilizes its amorphous structure is discussed based on the changes in the Raman signals of the TO, LO, and LA phonons during annealing. The characteristic bond length of the Ge atoms allows them to stabilize the random network of the amorphous Si composed of quasi-tetrahedral Si units, and obstruct its rearrangement.« less

Phase transformations in 40-60-GPa shocked gneisses from the Haughton Crater (Canada): An Analytical Transmission Electron Microscopy (ATEM) study

NASA Technical Reports Server (NTRS)

Martinez, I.; Guyot, F.; Schaerer, U.

1992-01-01

In order to better understand phase transformations, chemical migration, and isotopic disequilibrium in highly shocked rocks, we have performed a microprobe and an ATEM study on gneisses shocked up to 60 GPa from the Haughton Crater. This study reveals the following chemical and structural characteristics: (1) SiO2 dominant areas are formed by a mixture of pure SiO2 polycrystalline quartz identified by electron diffraction pattern and chemical analysis and a silica-rich amorphous phase containing minor amounts of aluminium, potassium, and iron; (2) Areas with biotitelike composition are formed by less than 200-nm grains of iron-rich spinels embedded in a silica-rich amorphous phase that is very similar to the one described above; (3) Layers with feldsparlike composition are constituted by 100-200-nm-sized alumina-rich grains (the indexation of the crystalline structure is under progress) and the silica-rich amorphous phase; (4) Zones characterized by the unusual Al/Si ratio close to 1 are formed by spinel grains (200-nm-sized) embedded in the same silica-rich amorphous phase; and (5) The fracturated sillimanites contain domains with a lamellar structure, defined by the intercalation of 100-nm-wide lamellae of mullite crystals and of a silica-rich amorphous phase. These mullite crystals preserved the crystallographical orientation of the preshock sillimanite. All compositional domains, identified at the microprobe scale, can thus be explained by a mixture in different proportion between the following phases: (1) a silica-rich amorphous phase, with minor Al and K; (2) quartz crystals; (3) spinel crystals and alumina-rich crystals; (4) sillimanite; and (5) mullite. Such mixtures of amorphous phases and crystals in different proportions explain disturbed isotope systems in these rocks and chemical heterogeneities observed on the microprobe.

Phase stability, porosity distribution and microstructural evolution of amorphous Al{sub 50}Ti{sub 50} powders consolidated by electrical resistance sintering

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

Urban, P., E-mail: purban@us.es; Montes, J. M.; Cintas, J.

2015-03-30

The effect of intensity and duration of the electrical resistance sintering process on the phase stability, porosity distribution and microstructural evolution of Al{sub 50}Ti{sub 50} amorphous powders is studied. The phase transformations during the consolidation process were determined by X-ray diffraction. The porosity distribution was observed by optical and scanning electron microscopy. The amorphous phase is partially transformed to the crystalline phase during the sintering process, and formation of AlTi and AlTi{sub 3} intermetallic compounds occurs for temperatures higher than 300 °C. Finally, it is observed that the compacts core have lower porosity and a higher tendency to the amorphous-crystallinemore » phase transformation than the periphery.« less

The Amorphous Composition of Three Mudstone Samples from Gale Crater: Implications for Weathering and Diagenetic Processes on Mars

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Downs, R. T.; Rampe, E. B.; Morris, R. V.; Bristow, T. F.; Ming, D. W.; Blake, D. F.; Vaniman, D. T.; Morrison, S. M.; Sutter, B.;

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.

Amorphization reaction in thin films of elemental Cu and Y

NASA Astrophysics Data System (ADS)

Johnson, R. W.; Ahn, C. C.; Ratner, E. R.

1989-10-01

Compositionally modulated thin films of Cu and Y were prepared in an ultrahigh-vacuum dc ion-beam deposition chamber. The amorphization reaction was monitored by in situ x-ray-diffraction measurements. Growth of amorphous Cu1-xYx is observed at room temperature with the initial formation of a Cu-rich amorphous phase. Further annealing in the presence of unreacted Y leads to Y enrichment of the amorphous phase. Growth of crystalline CuY is observed for T=469 K. Transmission-electron-microscopy measurements provide real-space imaging of the amorphous interlayer and growth morphology. Models are developed, incorporating metastable interfacial and bulk free-energy diagrams, for the early stage of the amorphization reaction.

Distortion of Local Atomic Structures in Amorphous Ge-Sb-Te Phase Change Materials

NASA Astrophysics Data System (ADS)

Hirata, A.; Ichitsubo, T.; Guan, P. F.; Fujita, T.; Chen, M. W.

2018-05-01

The local atomic structures of amorphous Ge-Sb-Te phase-change materials have yet to be clarified and the rapid crystal-amorphous phase change resulting in distinct optical contrast is not well understood. We report the direct observation of local atomic structures in amorphous Ge2Sb2Te5 using "local" reverse Monte Carlo modeling dedicated to an angstrom-beam electron diffraction analysis. The results corroborated the existence of local structures with rocksalt crystal-like topology that were greatly distorted compared to the crystal symmetry. This distortion resulted in the breaking of ideal octahedral atomic environments, thereby forming local disordered structures that basically satisfied the overall amorphous structure factor. The crystal-like distorted octahedral structures could be the main building blocks in the formation of the overall amorphous structure of Ge-Sb-Te.

Long-term oxidization and phase transition of InN nanotextures

PubMed Central

2011-01-01

The long-term (6 months) oxidization of hcp-InN (wurtzite, InN-w) nanostructures (crystalline/amorphous) synthesized on Si [100] substrates is analyzed. The densely packed layers of InN-w nanostructures (5-40 nm) are shown to be oxidized by atmospheric oxygen via the formation of an intermediate amorphous In-Ox-Ny (indium oxynitride) phase to a final bi-phase hcp-InN/bcc-In2O3 nanotexture. High-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy and selected area electron diffraction are used to identify amorphous In-Ox-Ny oxynitride phase. When the oxidized area exceeds the critical size of 5 nm, the amorphous In-Ox-Ny phase eventually undergoes phase transition via a slow chemical reaction of atomic oxygen with the indium atoms, forming a single bcc In2O3 phase. PMID:21711908

Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

PubMed

Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

2014-11-26

We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

Amorphous Calcium Carbonate Based-Microparticles for Peptide Pulmonary Delivery.

PubMed

Tewes, Frederic; Gobbo, Oliviero L; Ehrhardt, Carsten; Healy, Anne Marie

2016-01-20

Amorphous calcium carbonate (ACC) is known to interact with proteins, for example, in biogenic ACC, to form stable amorphous phases. The control of amorphous/crystalline and inorganic/organic ratios in inhalable calcium carbonate microparticles may enable particle properties to be adapted to suit the requirements of dry powders for pulmonary delivery by oral inhalation. For example, an amorphous phase can immobilize and stabilize polypeptides in their native structure and amorphous and crystalline phases have different mechanical properties. Therefore, inhalable composite microparticles made of inorganic (i.e., calcium carbonate and calcium formate) and organic (i.e., hyaluronan (HA)) amorphous and crystalline phases were investigated for peptide and protein pulmonary aerosol delivery. The crystalline/amorphous ratio and polymorphic form of the inorganic component was altered by changing the microparticle drying rate and by changing the ammonium carbonate and HA initial concentration. The bioactivity of the model peptide, salmon calcitonin (sCT), coprocessed with alpha-1-antitrypsin (AAT), a model protein with peptidase inhibitor activity, was maintained during processing and the microparticles had excellent aerodynamic properties, making them suitable for pulmonary aerosol delivery. The bioavailability of sCT after aerosol delivery as sCT and AAT-loaded composite microparticles to rats was 4-times higher than that of sCT solution.

Phosphor doping enhanced c-axis alignment and exchange decoupling of sputtered Co-Pt perpendicular thin films

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

Yang, Bo; Qin, Gaowu, E-mail: qingw@smm.neu.edu.cn; Xiao, Na

2016-04-14

In the present work, Co-23.0 at. % Pt and Co-23.0 at. % Pt-3.67 at. % P thin films with their c-axis perpendicular to the substrate surface were fabricated on a glass substrate by DC magnetron sputtering. X-ray diffraction and transmission electron microscopic analyses demonstrate that the doping of P improves the c-axis alignment and forms P-rich non-magnetic phase at grain boundary areas, the latter resulting in inter-granular exchange decoupling between Co-Pt grains. The improved c-axis alignment and the inter-granular exchange decoupling give rise to the increase of the out of plane coercivity and the squareness of the Co-Pt-P films.

Damage mechanisms in bithermal and thermomechanical fatigue of Haynes 188

NASA Technical Reports Server (NTRS)

Kalluri, Sreeramesh; Halford, Gary R.

1992-01-01

Post failure fractographic and metallographic studies were conducted on Haynes 188 specimens fatigued under bithermal and thermomechanical loading conditions between 316 and 760 C. Bithermal fatigue specimens examined included those tested under high strain rate in-phase and out-phase, tensile creep in-phase, and compressive creep out-of-phase loading conditions. Specimens tested under in-phase and out-of-phase thermomechanical fatigue were also examined. The nature of failure mode (transgrandular versus intergranular), the topography of the fracture surface, and the roles of oxidation and metallurgical changes were studied for each type of bithermal and thermomechanical test.

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper-niobium system

NASA Astrophysics Data System (ADS)

Puthucode, A.; Devaraj, A.; Nag, S.; Bose, S.; Ayyub, P.; Kaufman, M. J.; Banerjee, R.

2014-05-01

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu-Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200 °C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300 °C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.

In situ observation of shear-driven amorphization in silicon crystals

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

He, Yang; Zhong, Li; Fan, Feifei

Amorphous materials have attracted great interest in the scientific and technological fields. An amorphous solid usually forms under the externally driven conditions of melt-quenching, irradiation and severe mechanical deformation. However, its dynamic formation process remains elusive. Here we report the in situ atomic-scale observation of dynamic amorphization processes during mechanical straining of nanoscale silicon crystals by high resolution transmission electron microscopy (HRTEM). We observe the shear-driven amorphization (SDA) occurring in a dominant shear band. The SDA involves a sequence of processes starting with the shear-induced diamond-cubic to diamond-hexagonal phase transition that is followed by dislocation nucleation and accumulation in themore » newly formed phase, leading to the formation of amorphous silicon. The SDA formation through diamond-hexagonal phase is rationalized by its structural conformity with the order in the paracrystalline amorphous silicon, which maybe widely applied to diamond-cubic materials. Besides, the activation of SDA is orientation-dependent through the competition between full dislocation nucleation and partial gliding.« less

TEM Study of Intergranular Fluid Distributions in Rocks at a Nanometer Scale

NASA Astrophysics Data System (ADS)

Hiraga, T.; Anderson, I. M.; Kohlstedt, D. L.

2002-12-01

The distribution of intergranular fluids in rocks plays an essential role in fluid migration and rock rheology. Structural and chemical analyses with sub-nanometer resolution is possible with transmission and scanning-transmission electron microscopy; therefore, it is possible to perform the fine-scale structural analyses required to determine the presence or absence of very thin fluid films along grain boundaries. For aqueous fluids in crustal rocks, Hiraga et al. (2001) observed a fluid morphology controlled by the relative values of the solid-solid and solid-fluid interfacial energies, which resulted in well-defined dihedral angles. Their high-resolution transmission electron microscopy (TEM) observations demonstrate that grain boundaries are tight even at a nanometer scale, consistent with the absence of aqueous fluid films. For partially molten ultra-mafic rocks, two conflicting conclusions have been reached: nanometer-thick melt films wet grain boundaries (Drury and Fitz Gerald 1996; De Kloe et al. 2000) versus essentially all grain boundaries are melt-free (Vaughan et al. 1982; Kohlstedt 1990). To resolve this conflict, Hiraga et al. (2002) examined grain boundaries in quenched partially molten peridotites. Their observations demonstrate the following: (i) Although a small fraction of the grains are separated by relatively thick (~1 μm) layers of melt, lattice fringe images obtained with a high-resolution TEM reveal that most of the remaining boundaries do not contain a thin amorphous phase. (ii) In addition, the composition of olivine-olivine grain boundaries was analyzed with a nano-beam analytical scanning TEM with a probe size of <2 nm. Although the grain boundaries contained no melt film, the concentration of Ca, Al and Ti were enhanced near the boundaries. The segregation of these elements to the grain boundaries formed enriched regions <7 nm wide. A similar pattern of chemical segregation was detected in subsolidus systems. Creep experiments on the partially molten rocks that were analyzed in this study reveal little weakening even at melt contents approaching 4 vol%, consistent with our observations of melt-free grain boundaries.

Multivariate Quantification of the Solid State Phase Composition of Co-Amorphous Naproxen-Indomethacin.

PubMed

Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S

2015-10-27

To benefit from the optimized dissolution properties of active pharmaceutical ingredients in their amorphous forms, co-amorphisation as a viable tool to stabilize these amorphous phases is of both academic and industrial interest. Reports dealing with the physical stability and recrystallization behavior of co-amorphous systems are however limited to qualitative evaluations based on the corresponding X-ray powder diffractograms. Therefore, the objective of the study was to develop a quantification model based on X-ray powder diffractometry (XRPD), followed by a multivariate partial least squares regression approach that enables the simultaneous determination of up to four solid state fractions: crystalline naproxen, γ-indomethacin, α-indomethacin as well as co-amorphous naproxen-indomethacin. For this purpose, a calibration set that covers the whole range of possible combinations of the four components was prepared and analyzed by XRPD. In order to test the model performances, leave-one-out cross validation was performed and revealed root mean square errors of validation between 3.11% and 3.45% for the crystalline molar fractions and 5.57% for the co-amorphous molar fraction. In summary, even four solid state phases, involving one co-amorphous phase, can be quantified with this XRPD data-based approach.

Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

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

Somrani, Saida; Banu, Mihai; Jemal, Mohamed

2005-05-15

The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatiticmore » phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO{sub 4}{sup 2-} ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings.« less

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.

Microstructures, magnetic properties and coercivity mechanisms of Nd-Ce-Fe-B based alloys by Zr substitution

NASA Astrophysics Data System (ADS)

Wang, Lei; Quan, Qichen; Zhang, Lili; Hu, Xianjun; Ur Rehman, Sajjad; Jiang, Qingzheng; Du, Junfeng; Zhong, Zhenchen

2018-03-01

In this paper, the effects of Zr addition on microstructures, magnetic properties, exchange coupling, and coercivity mechanisms of Nd-Ce-Fe-B alloys fabricated by melt-spinning technique are investigated. It is found that the coercivity Hcj is enhanced significantly by Zr substitution in the (Nd0.8Ce0.2)13Fe82-xZrxB5 alloys, while the remanence Jr is reduced slightly. The Hcj increases from 12.2 to 13.7 kOe by adding Zr up to 1.5 at. %, whereas Hcj is decreased with a further increase in Zr content. The larger lattice constants and unit cell volumes of the matrix phase indicate that Zr atoms enter into the hard magnetic phase by substituting Fe sites. The reduction of Tc implies the attenuation of the exchange interaction in the 2:14:1 phase with Zr occupying the Fe sites. The weakened intergranular exchange coupling of the Zr added alloy may be attributed to the formation of a non-magnetic intergranular phase. It is worth noting that the coercivity is dominated by the pinning of domain walls at defect positions even though the nucleation of reversal domains still exists. The synergistic function between the pinning effect and the exchange coupling leads to improved magnetic properties.

Amorphization dynamics of Ge{sub 2}Sb{sub 2}Te{sub 5} films upon nano- and femtosecond laser pulse irradiation

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

Siegel, J.; Gawelda, W.; Puerto, D.

2008-01-15

Phase transformations of crystalline Ge{sub 2}Sb{sub 2}Te{sub 5} films upon pulsed laser irradiation have been studied using in situ reflectivity measurements with temporal resolution. Two different configurations allowed point probing with nanosecond temporal resolution and imaging with subpicosecond temporal and micrometer spatial resolution. The role of the pulse duration and laser fluence on the dynamics of the phase change and the degree of amorphization is discussed. Several advantageous features of femtosecond compared to nanosecond laser-induced amorphization are identified. Moreover, a high-resolution study of the amorphization dynamics reveals the onset of amorphization at moderate fluences to occur within {approx}100 ps aftermore » arrival of the laser pulse. At high fluences, amorphization occurs after {approx}430 ps and the molten phase is characterized by an anomalously low reflectivity value, indicative of a state of extreme supercooling.« less

Constructing first-principles phase diagrams of amorphous LixSi using machine-learning-assisted sampling with an evolutionary algorithm

NASA Astrophysics Data System (ADS)

Artrith, Nongnuch; Urban, Alexander; Ceder, Gerbrand

2018-06-01

The atomistic modeling of amorphous materials requires structure sizes and sampling statistics that are challenging to achieve with first-principles methods. Here, we propose a methodology to speed up the sampling of amorphous and disordered materials using a combination of a genetic algorithm and a specialized machine-learning potential based on artificial neural networks (ANNs). We show for the example of the amorphous LiSi alloy that around 1000 first-principles calculations are sufficient for the ANN-potential assisted sampling of low-energy atomic configurations in the entire amorphous LixSi phase space. The obtained phase diagram is validated by comparison with the results from an extensive sampling of LixSi configurations using molecular dynamics simulations and a general ANN potential trained to ˜45 000 first-principles calculations. This demonstrates the utility of the approach for the first-principles modeling of amorphous materials.

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.

High-pressure phase transitions, amorphization, and crystallization behaviors in Bi2Se3.

PubMed

Zhao, Jinggeng; Liu, Haozhe; Ehm, Lars; Dong, Dawei; Chen, Zhiqiang; Gu, Genda

2013-03-27

The phase transition, amorphization, and crystallization behaviors of the topological insulator bismuth selenide (Bi2Se3) were discovered by performing in situ high-pressure angle-dispersive x-ray diffraction experiments during an increasing, decreasing, and recycling pressure process. In the compression process, Bi2Se3 transforms from the original rhombohedral structure (phase I(A)) to a monoclinic structure (phase II) at about 10.4 GPa, and further to a body-centered tetragonal structure (phase III) at about 24.5 GPa. When releasing pressure to ambient conditions after the complete transformation from phase II to III, Bi2Se3 becomes an amorphous solid (AM). In the relaxation process from this amorphous state, Bi2Se3 starts crystallizing into an orthorhombic structure (phase I(B)) about five hours after releasing the pressure to ambient. A review of the pressure-induced phase transition behaviors of A2B3-type materials composed from the V and VI group elements is presented.

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

Zhang, Kezhao; Ni, Longchang; Lei, Zhenglong, E-ma

The tensile deformation behavior of laser welded Ti{sub 2}AlNb joints was investigated using in situ analysis methods. The fracture mode of the single-B2-phase fusion zone was quasi-cleavage at room temperature and intergranular at 650 °C, while that of base metal was microvoid coalescence at both room temperature and 650 °C. Tensile deformation at room temperature was observed using in situ SEM tensile testing. In base metal, microcracks nucleated and propagated mainly within the O phase or along O/B2 phase boundaries. While both the cross- and multi-slips were found in the single-B2-phase fusion zone, a confocal laser scanning microscopy was usedmore » to observe the crack initiation and propagation process in situ at 650 °C. Cracks mainly formed along the B2/O phase boundaries in base metal, along the fragile grain boundaries of B2 phase in the fusion zone. The thermal simulation experiment and following TEM analysis indicated that the precipitation of continuous O-phase films along the B2 grain boundaries resulted in the high temperature brittleness of laser welded Ti{sub 2}AlNb joints. - Highlights: •Cracks formed within O phase or along B2/O boundaries in the base metal. •Cross- and multi-slips relieved stress in the fusion zone at room temperature. •Cracks mainly formed along the B2/O boundaries at 650 °C. •In the fusion zone, intergranular cracks were in situ observed at 650 °C. •O-phase films along B2 grain boundaries caused the high temperature brittleness.« less

Solid-State NMR Investigation of Drug-Excipient Interactions and Phase Behavior in Indomethacin-Eudragit E Amorphous Solid Dispersions.

PubMed

Lubach, Joseph W; Hau, Jonathan

2018-02-20

To investigate the nature of drug-excipient interactions between indomethacin (IMC) and methacrylate copolymer Eudragit® E (EE) in the amorphous state, and evaluate the effects on formulation and stability of these amorphous systems. Amorphous solid dispersions containing IMC and EE were spray dried with drug loadings from 20% to 90%. PXRD was used to confirm the amorphous nature of the dispersions, and DSC was used to measure glass transition temperatures (T g ). 13 C and 15 N solid-state NMR was utilized to investigate changes in local structure and protonation state, while 1 H T 1 and T 1ρ relaxation measurements were used to probe miscibility and phase behavior of the dispersions. T g values for IMC-EE solid dispersions showed significant positive deviations from predicted values in the drug loading range of 40-90%, indicating a relatively strong drug-excipient interaction. 15 N solid-state NMR exhibited a change in protonation state of the EE basic amine, with two distinct populations for the EE amine at -360.7 ppm (unprotonated) and -344.4 ppm (protonated). Additionally, 1 H relaxation measurements showed phase separation at high drug load, indicating an amorphous ionic complex and free IMC-rich phase. PXRD data showed all ASDs up to 90% drug load remained physically stable after 2 years. 15 N solid-state NMR experiments show a change in protonation state of EE, indicating that an ionic complex indeed forms between IMC and EE in amorphous solid dispersions. Phase behavior was determined to exhibit nanoscale phase separation at high drug load between the amorphous ionic complex and excess free IMC.

Grain boundaries structures and wetting in doped silicon, nickel and copper

NASA Astrophysics Data System (ADS)

Meshinchi Asl, Kaveh

This thesis reports a series of fundamental investigations of grain boundary wetting, adsorption and structural (phases) transitions in doped Ni, Cu and Si with technological relevance to liquid metal embrittlement, liquid metal corrosion and device applications. First, intrinsically ductile metals are prone to catastrophic failure when exposed to certain liquid metals, but the atomic level mechanism for this effect is not fully understood. A nickel sample infused with bismuth atoms was characterized and a bilayer interfacial phase that is the underlying cause of embrittlement was observed. In a second related study, we showed that addition of minor impurities can significantly enhance the intergranular penetration of bismuth based liquids in polycrystalline nickel and copper, thereby increasing the liquid metal corrosion rates. Furthermore, we extended a concept that was initially proposed in the Rice-Wang model for grain boundary embrittlement to explain our observations of the impurity-enhanced intergranular penetration of liquid metals. Finally, a grain-boundary transition from a bilayer to an intrinsic is observed in the Si-Au system. This observation directly shows that a grain boundary can exhibit a first-order "phase" transition, which often implies abrupt changes in properties.

A study on the morphology of polystyrene-grafted poly(ethylene-alt-tetrafluoroethylene) (ETFE) films prepared using a simultaneous radiation grafting method

NASA Astrophysics Data System (ADS)

Song, Ju-Myung; Ko, Beom-Seok; Sohn, Joon-Yong; Nho, Young Chang; Shin, Junhwa

2014-04-01

The morphology of polystyrene-grafted poly(ethylene-alt-tetrafluoroethylene) (ETFE) films prepared using a simultaneous radiation grafting method was investigated using DMA, DSC, XRD, and SAXS instruments. The DMA study indicates that the ETFE amorphous phase and PS amorphous phase are mixed well in the PS-grafted ETFE films while the ETFE crystalline phase and the PS amorphous phase are separated, suggesting that the PS chains are grafted mainly on the ETFE amorphous regions. The DSC and XRD data showed that the natural crystalline structures of ETFE in the grafted ETFE films are not affected by the degree of grafting. The SAXS profiles displayed that the inter-crystalline distance of the ETFE films increases with an increasing degree of grafting, which further implies that the PS graft chains formed by the simultaneous irradiation has a significant impact on the amorphous morphology of the resulting grafted ETFE film. Thus, these results indicate that the styrene monomers are mainly grafted on the ETFE amorphous regions during the simultaneous radiation grafting process.

Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

NASA Astrophysics Data System (ADS)

Kim, H.; McIntyre, P. C.

2002-11-01

Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

Environmentally induced crack propagation in Inconel alloys 600 and 690 under hydrogen supersaturated steam

NASA Astrophysics Data System (ADS)

Ali, Mehboob Muzzammil

Intergranular stress corrosion cracking (IGSCC) of Inconel alloys 600 and 690 was investigated by exposing them to 300--400°C in deaerated hydrogen supersaturated steam. Crack growth rates were measured in-situ for the above alloys using modified wedge-opening-loaded (M-WOL) linear elastic fracture specimens under constant displacement conditions. The applied stress intensity factors (K) used varied from 29--90 MPam1/2. An activation energy of 120 kJ/mol was found for crack growth rates as a function of temperature. This activation energy is close to the one corresponding to grain boundary self diffusion of nickel. In addition, it was found that the apparent crack growth rates (da/dt) exhibited a linear dependence with KI, given by (da/dt) = A.KIn, where n = 1 in our case. Microstructurally, crack propagation in both the alloys was predominantly along the grain boundaries. It is suggested that high fugacity hydrogen was generated at the tip of the crack, as a result of the reaction of H2O with Cr2O3 on the fracture surface leading to IGSCC. It was found that the rates of crack propagation in both alloys 600 and 690 are very similar. Moreover, under the applied KIs, both alloys 600 and 690 show a similar tendency to crack intergranularly in a direction perpendicular to the applied stress. Crack branching was also exhibited by both the alloys 600 as well as 690. The difference in the crack growth rates of alloys 600 and 690 was found to be only about 2%, which indicates that the crack growth rates in these alloys is independent of the alloy chromium content and that, possibly very similar crack growth mechanisms are active in both the alloys 600 and 690 under similar conditions of KI and temperature. HREM images at the crack tip of alloy 690 exhibit two distinct regions---a crystalline region, and an adjacent amorphous region, which is likely to be either a hydroxide or an amorphous oxide layer. This layer is expected to result from passivation reactions as the crack surface is exposed to the corrosive environment.

Chain Confinement in Electrospun Nanocomposites: using Thermal Analysis to Investigate Polymer-Filler Interactions

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

Q Ma; B Mao; P Cebe

2011-12-31

We investigate the interaction of the polymer matrix and filler in electrospun nanofibers using advanced thermal analysis methods. In particular, we study the ability of silicon dioxide nanoparticles to affect the phase structure of poly(ethylene terephthalate), PET. SiO{sub 2} nanoparticles (either unmodified or modified with silane) ranging from 0 to 2.0 wt% in PET were electrospun from hexafluoro-2-propanol solutions. The morphologies of both the electrospun (ES) nanofibers and the SiO{sub 2} powders were observed by scanning and transmission electron microscopy, while the amorphous or crystalline nature of the fibers was determined by real-time wide-angle X-ray scattering. The fractions of themore » crystal, mobile amorphous, and rigid amorphous phases of the non-woven, nanofibrous composite mats were quantified by using heat capacity measurements. The amount of the immobilized polymer layer, the rigid amorphous fraction, was obtained from the specific reversing heat capacity for both as-spun amorphous fibers and isothermally crystallized fibers. Existence of the rigid amorphous phase in the absence of crystallinity was verified in nanocomposite fibers, and two origins for confinement of the rigid amorphous fraction are proposed. Thermal analysis of electrospun fibers, including quasi-isothermal methods, provides new insights to quantitatively characterize the polymer matrix phase structure and thermal transitions, such as devitrification of the rigid amorphous fraction.« less

Rate-Dependent Behavior of the Amorphous Phase of Spider Dragline Silk

PubMed Central

Patil, Sandeep P.; Markert, Bernd; Gräter, Frauke

2014-01-01

The time-dependent stress-strain behavior of spider dragline silk was already observed decades ago, and has been attributed to the disordered sequences in silk proteins, which compose the soft amorphous matrix. However, the actual molecular origin and magnitude of internal friction within the amorphous matrix has remained inaccessible, because experimentally decomposing the mechanical response of the amorphous matrix from the embedded crystalline units is challenging. Here, we used atomistic molecular dynamics simulations to obtain friction forces for the relative sliding of peptide chains of Araneus diadematus spider silk within bundles of these chains as a representative unit of the amorphous matrix in silk fibers. We computed the friction coefficient and coefficient of viscosity of the amorphous phase to be in the order of 10−6 Ns/m and 104 Ns/m2, respectively, by extrapolating our simulation data to the viscous limit. Finally, we used a finite element method for the amorphous phase, solely based on parameters derived from molecular dynamics simulations including the newly determined coefficient of viscosity. With this model the time scales of stress relaxation, creep, and hysteresis were assessed, and found to be in line with the macroscopic time-dependent response of silk fibers. Our results suggest the amorphous phase to be the primary source of viscosity in silk and open up the avenue for finite element method studies of silk fiber mechanics including viscous effects. PMID:24896131

Ice polyamorphism in the minimal Mercedes-Benz model of water.

PubMed

Cartwright, Julyan H E; Piro, Oreste; Sánchez, Pedro A; Sintes, Tomás

2012-12-28

We investigate ice polyamorphism in the context of the two-dimensional Mercedes-Benz model of water. We find a first-order phase transition between a crystalline phase and a high-density amorphous phase. Furthermore, we find a reversible transformation between two amorphous structures of high and low density; however, we find this to be a continuous and not an abrupt transition, as the low-density amorphous phase does not show structural stability. We discuss the origin of this behavior and its implications with regard to the minimal generic modeling of polyamorphism.

Ice polyamorphism in the minimal Mercedes-Benz model of water

NASA Astrophysics Data System (ADS)

Cartwright, Julyan H. E.; Piro, Oreste; Sánchez, Pedro A.; Sintes, Tomás

2012-12-01

We investigate ice polyamorphism in the context of the two-dimensional Mercedes-Benz model of water. We find a first-order phase transition between a crystalline phase and a high-density amorphous phase. Furthermore, we find a reversible transformation between two amorphous structures of high and low density; however, we find this to be a continuous and not an abrupt transition, as the low-density amorphous phase does not show structural stability. We discuss the origin of this behavior and its implications with regard to the minimal generic modeling of polyamorphism.

Pressure-Induced Phase Transitions in GeTe-Rich Ge-Sb-Te Alloys across the Rhombohedral-to-Cubic Transitions.

PubMed

Krbal, Milos; Bartak, Jaroslav; Kolar, Jakub; Prytuliak, Anastasiia; Kolobov, Alexander V; Fons, Paul; Bezacier, Lucile; Hanfland, Michael; Tominaga, Junji

2017-07-17

We demonstrate that pressure-induced amorphization in Ge-Sb-Te alloys across the ferroelectric-paraelectric transition can be represented as a mixture of coherently distorted rhombohedral Ge 8 Sb 2 Te 11 and randomly distorted cubic Ge 4 Sb 2 Te 7 and high-temperature Ge 8 Sb 2 Te 11 phases. While coherent distortion in Ge 8 Sb 2 Te 11 does not prevent the crystalline state from collapsing into its amorphous counterpart in a similar manner to pure GeTe, the pressure-amorphized Ge 8 Sb 2 Te 11 phase begins to revert to the crystalline cubic phase at ∼9 GPa in contrast to Ge 4 Sb 2 Te 7 , which remains amorphous under ambient conditions when gradually decompressed from 40 GPa. Moreover, experimentally, it was observed that pressure-induced amorphization in Ge 8 Sb 2 Te 11 is a temperature-dependent process. Ge 8 Sb 2 Te 11 transforms into the amorphous phase at ∼27.5 and 25.2 GPa at room temperature and 408 K, respectively, and completely amorphizes at 32 GPa at 408 K, while some crystalline texture could be seen until 38 GPa (the last measurement point) at room temperature. To understand the origins of the temperature dependence of the pressure-induced amorphization process, density functional theory calculations were performed for compositions along the (GeTe) x - (Sb 2 Te 3 ) 1-x tie line under large hydrostatic pressures. The calculated results agreed well with the experimental data.

Role of oxygen diffusion at Ni/Cr2O3 interface in intergranular oxidation of Ni-Cr alloy

NASA Astrophysics Data System (ADS)

Medasani, Bharat; Sushko, Maria; Schreiber, Daniel; Rosso, Kevin; Bruemmer, Stephen

Certain Ni-Cr alloys used in nuclear systems experience intergranular oxidation and stress corrosion cracking when exposed to high-temperature water leading to their degradation and unexpected failure. To develop a mechanistic understanding of grain boundary oxidation processes, we proposed a mesoscale metal alloy oxidation model that combines quantum Density Functional Theory (DFT) with mesoscopic Poisson-Nernst-Planck/classical DFT. This framework encompasses the chemical specificity of elementary diffusion processes and mesoscale reactive dynamics, and allows modeling oxidation processes on experimentally relevant length scales from first principles. As a proof of concept, a preliminary model was previously employed that limited oxygen diffusion pathways to those through the oxide phase and did not allow oxygen diffusion in the alloy or across oxide/alloy interfaces. In this work, we expand the model to include oxygen diffusion pathways along Ni/Cr2O3 interfaces and demonstrate the increasing importance of such pathways for intergranular oxidation of Ni-Cr alloys with high Cr content. This work is supported by the U.S. Dept. of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Simulations are performed using PNNL Institutional Computing facility.

Exploring Molecular Speciation and Crystallization Mechanism of Amorphous 2-Phenylamino Nicotinic Acid.

PubMed

Kalra, Arjun; Lubach, Joseph W; Munson, Eric J; Li, Tonglei

2018-02-07

Molecular understanding of phase stability and transition of the amorphous state helps in formulation and manufacturing of poorly-soluble drugs. Crystallization of a model compound, 2-phenylamino nicotinic acid (2PNA), from the amorphous state was studied using solid-state analytical methods. Our previous report suggests that 2PNA molecules mainly develop intermolecular -COOH∙∙∙pyridine N (acid-pyridine) interactions in the amorphous state. In the current study, the molecular speciation is explored with regard to the phase transition from the amorphous to the crystalline state. Using spectroscopic techniques, the molecular interactions and structural evolvement during the recrystallization from the glassy state were investigated. The results unveiled that the structurally heterogeneous amorphous state contains acid-pyridine aggregates - either as hydrogen-bonded neutral molecules or as zwitterions - as well as a population of carboxylic acid dimers. Phase transition from the amorphous state results in crystal structures composed of carboxylic acid dimer (acid-acid) synthon or acid-pyridine chains depending on the crystallization conditions employed. The study underlines the structural evolvement, as well as its impact on the metastability, of amorphous samples from local, supramolecular assemblies to long-range intermolecular ordering through crystallization.

Effect of amorphous phases during the hydraulic conversion of α-TCP into calcium-deficient hydroxyapatite.

PubMed

Hurle, Katrin; Neubauer, Juergen; Bohner, Marc; Doebelin, Nicola; Goetz-Neunhoeffer, Friedlinde

2014-09-01

Powders of α-tricalcium phosphate (α-TCP), which readily react with water to form calcium-deficient hydroxyapatite (CDHA), are frequently used in bone cements. As, for clinical applications, it is important to adjust the setting reaction of the cements to a reasonable reaction time, exact knowledge of the hydration mechanism is essential. It is known that prolonged milling results in partial amorphization of α-TCP powders and that dissolution of the amorphous phase significantly accelerates the hydration, but it is not clear yet when the amorphous phase reacts in comparison to the crystalline α-TCP. Therefore the aim of this study was to investigate the development of quantitative phase content of α-TCP samples during hydration. For this purpose, three α-TCP powders, containing 0, 16 and 71wt.% of amorphous phase (ATCP), were mixed with either deionized water or a 0.1M Na2HPO4 aqueous solution. The crystalline evolution of the paste was assessed quantitatively during the first 48h of hydration at 23°C by G-factor quantification. The present investigations demonstrate that ATCP reacted earlier than crystalline α-TCP. The results also suggest the formation of an X-ray amorphous phase during the hydraulic conversion formation of α-TCP into CDHA. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Evidence for stable grain boundary melt films in experimentally deformed olivine-orthopyroxene rocks

NASA Astrophysics Data System (ADS)

de Kloe, R.; Drury, M. R.; van Roermund, H. L. M.

The microstructure of olivine-olivine grain boundaries has been studied in experimentally deformed (1200-1227°C, 300MPa) partially molten olivine and olivine-orthopyroxene rocks. In-situ melting produced 1vol% melt in all samples studied. Grain boundary analyses were carried out using a number of transmission electron microscopy techniques. The grain boundary chemistry in undeformed olivine-orthopyroxene starting material showed evidence for the presence of an intergranular phase along some, but not all, of the olivine-olivine boundaries. In the deformed samples, ultrathin Si-rich, Al- and Ca-bearing amorphous films have been observed along all investigated olivine-olivine grain boundaries. The chemistry of the grain boundaries, which is considered to be indicative for the presence of a thin film, was measured with energy-dispersive X-ray spectroscopy (EDX) and energy-filtering imaging. The amorphous nature of the films was confirmed with diffuse dark field imaging, Fresnel fringe imaging, and high-resolution electron microscopy. The films range in thickness from 0.6 to 3.0nm, and EDX analyses show that the presence of Al and Ca is restricted to this ultrathin film along the grain boundaries. Because thin melt films have been observed in all the samples, they are thought to be stable features of the melt microstructure in deformed partially molten rocks. The transition from the occasional presence of films in the undeformed starting material to the general occurrence of the films in deformed materials suggests that deformation promotes the formation and distribution of the films. Alternatively, hot-pressing may be too short for films to develop along all grain boundaries. A difference in creep strength between the studied samples could not be attributed to grain boundary melt films, as these have been found in all deformed samples. However, a weakening effect of grain boundary melt films on olivine rheology could not be ruled out due to the lack of confirmed melt-film free experiments.

The liquid⟷amorphous transition and the high pressure phase diagram of carbon

NASA Astrophysics Data System (ADS)

Robinson, David R.; Wilson, Mark

2013-04-01

The phase diagram of carbon is mapped to high pressure using a computationally-tractable potential model. The use of a relatively simple (Tersoff-II) potential model allows a large range of phase space to be explored. The coexistence (melting) curve for the diamond crystal/liquid dyad is mapped directly by modelling the solid/liquid interfaces. The melting curve is found to be re-entrant and belongs to a conformal class of diamond/liquid coexistence curves. On supercooling the liquid a phase transition to a tetrahedral amorphous form (ta-C) is observed. The liquid ⟷ amorphous coexistence curve is mapped onto the pT plane and is found to also be re-entrant. The entropy changes for both melting and the amorphous ⟶ liquid transitions are obtained from the respective coexistence curves and the associated changes in molar volume. The structural change on amorphization is analysed at different points on the coexistence curve including for transitions that are both isochoric and isocoordinate (no change in nearest-neighbour coordination number). The conformal nature of the melting curve is highlighted with respect to the known behaviour of Si. The relationship of the observed liquid/amorphous coexistence curve to the Si low- and high-density amorphous (LDA/HDA) transition is discussed.

Pressure-induced silica quartz amorphization studied by iterative stochastic surface walking reaction sampling.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-02-08

The crystal to amorphous transformation is a common phenomenon in Nature and has important impacts on material properties. Our current knowledge on such complex solid transformation processes is, however, limited because of their slow kinetics and the lack of long-range ordering in amorphous structures. To reveal the kinetics in the amorphization of solids, this work, by developing iterative reaction sampling based on the stochastic surface walking global optimization method, investigates the well-known crystal to amorphous transformation of silica (SiO 2 ) under external pressures, the mechanism of which has long been debated for its non-equilibrium, pressure-sensitive kinetics and complex product components. Here we report for the first time the global potential energy surface (PES) and the lowest energy pathways for α-quartz amorphization from first principles. We show that the pressurization at 15 GPa, the reaction condition, can lift the quartz phase energetically close to the amorphous zone, which thermodynamically initializes the amorphization. More importantly, the large flexibility of Si cation coordination (including four, five and six coordination) results in many kinetically competing routes to more stable dense forms, including the known MI, stishovite, newly-identified MII and TI phases. All these pathways have high barriers due to the local Si-O bond breaking and are mediated by amorphous structures with five-fold Si. This causes simultaneous crystal-to-crystal and crystal-to-amorphous transitions. The high barrier and the reconstructive nature of the phase transition are the key kinetics origin for silica amorphization under pressures.

Glass transitions and physical aging of cassava starch - corn oil blends.

PubMed

Pérez, Adriana; Sandoval, Aleida J; Cova, Aura; Müller, Alejandro J

2014-05-25

Glass transition temperatures and physical aging of amorphous cassava starch and their blends with corn oil were assessed by differential scanning calorimetry (DSC). Two enthalpic relaxation endotherms, well separated in temperature values, were exhibited by neat amorphous cassava starch with 10.6% moisture content, evidencing two amorphous regions within the starch with different degrees of mobility. The phase segregation of these two amorphous regions was favored by added corn oil at low moisture contents during storage. The presence of amylose-lipid complexes in this matrix, may also affect the molecular dynamics of these two amorphous regions at low moisture contents. Increasing moisture content, leads to a homogeneous amorphous phase, with an aging process characterized by a single enthalpic relaxation peak. In all cases, after deleting the thermal history of the samples only one glass transition temperature was detected (during DSC second heating runs) indicating that a single homogeneous amorphous phase was attained after erasing the effects of physical aging. Trends of the enthalpic relaxation parameters were also different at the two moisture contents considered in this work. Copyright © 2014 Elsevier Ltd. All rights reserved.

Bauschinger Effect in an Austenitic Steel: Neutron Diffraction and a Multiscale Approach

NASA Astrophysics Data System (ADS)

Fajoui, Jamal; Gloaguen, David; Legrand, Vincent; Oum, Guy; Kelleher, Joe; Kockelmann, Winfried

2016-05-01

The generation of internal stresses/strains arising from mechanical deformations in single-phase engineering materials was studied. Neutron diffraction measurements were performed to study the evolution of intergranular strains in austenitic steel during sequential loadings. Intergranular strains expand due to incompatibilities between grains and also resulting from single-crystal elastic and plastic anisotropy. A two-level homogenization approach was adopted in order to predict the mechanical state of deformed polycrystals in relation to the microstructure during Bauschinger tests. A mechanical description of the grain was developed through a micro-meso transition based on the Kröner model. The meso-macro transition using a self-consistent approach was applied to deduce the global behavior. Mechanical tests and neutron diffraction measurements were used to validate and assess the model.

The effect of microstructure on 650 C fatigue crack growth in P/M Astroloy

NASA Technical Reports Server (NTRS)

Gayda, J.; Miner, R. V.

1983-01-01

The effect of microstructure on fatigue crack propagation at 650 C has been studied in a P/M nickel-base superalloy, Astroloy. Crack propagation data were obtained in air and vacuum at 20 cpm with a modified compact tension specimen. The rate of crack growth, da/dn, was correlated with the stress intensity range. Key microstructural variables examined were grain size and the distribution and size of the strengthening gamma prime phase. A fine grain size less than 20 microns always promoted rapid, intergranular failure, while a large grain size promoted slower, transgranular failure which decreased as the size and volume fraction of aging gamma prime was manipulated so as to increase alloy strength. The rapid, intergranular mode of failure of the fine grain microstructures was suppressed in vacuum.

First-principles study of the liquid and amorphous phases of In2Te3

NASA Astrophysics Data System (ADS)

Dragoni, D.; Gabardi, S.; Bernasconi, M.

2017-08-01

Structural, dynamical, and electronic properties of the liquid and amorphous phase of the In2Te3 compound have been studied by means of density functional molecular dynamics simulations. This system is of interest as a phase change material, undergoing a fast and reversible change between the crystalline and amorphous phases upon heating. It can be seen as a constituent of ternary InSbTe alloys which are receiving attention for application in electronic phase change memories. Amorphous models of In2Te3 300 -atom large have been generated by quenching from the melt by using different exchange and correlation functionals and different descriptions of the van der Waals interaction. It turns out the local bonding geometry of the amorphous phase is mostly tetrahedral with corner and edge sharing tetrahedra similar to those found in the crystalline phases of the InTe, In2Te3 , and In2Te5 compounds. Benchmark calculations on the crystalline α phase of In2Te3 in the defective zincblend geometry have also been performed. The calculations reveal that the high symmetric F 4 ¯3 m structure inferred experimentally from x-ray diffraction for the α phase must actually result from a random distribution of Te-Te bonds in different octahedral cages formed by the coalescence of vacancies in the In sublattice.

Electron irradiation induced phase separation in a sodium borosilicate glass

NASA Astrophysics Data System (ADS)

Sun, K.; Wang, L. M.; Ewing, R. C.; Weber, W. J.

2004-06-01

Electron irradiation induced phase separation in a sodium borosilicate glass was studied in situ by analytical electron microscopy. Distinctly separate phases that are rich in boron and silicon formed at electron doses higher than 4.0 × 10 11 Gy during irradiation. The separated phases are still in amorphous states even at a much high dose (2.1 × 10 12 Gy). It indicates that most silicon atoms remain tetrahedrally coordinated in the glass during the entire irradiation period, except some possible reduction to amorphous silicon. The particulate B-rich phase that formed at high dose was identified as amorphous boron that may contain some oxygen. Both ballistic and ionization processes may contribute to the phase separation.

Addressing the amorphous content issue in quantitative phase analysis: the certification of NIST standard reference material 676a.

PubMed

Cline, James P; Von Dreele, Robert B; Winburn, Ryan; Stephens, Peter W; Filliben, James J

2011-07-01

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum (α-Al(2)O(3)) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Under the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% ± 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.

Shock wave induced phase transition in α -FePO 4

NASA Astrophysics Data System (ADS)

Joshi, K. D.; Suresh, N.; Jyoti, G.; Kulshreshtha, S. K.; Gupta, S. C.; Sikka, S. K.

Shock wave induced response of the berlinite form of FePO 4 has been investigated up to 8.5 GPa. The X-ray diffraction measurements on the shock recovered samples reveal transition to the mixture of an amorphous phase and an orthorhombic phase around 5 GPa. The proportion of the amorphous material in the recovered sample is found to decrease at higher pressure. The results are interpreted in terms of a three-level free energy diagram for the crystal to amorphous transitions.

The mobility and distribution of heavy metals during the formation of first cycle red beds.

USGS Publications Warehouse

Zielinski, R.A.; Bloch, S.; Walker, T.R.

1983-01-01

Analysis of the heavy metal content in a Holocene-Pliocene red bed sequence near San Felipe in N Baja California, Mexico, has yielded new information on the mobility and distribution of these metals during ageing of iron oxyhydroxides from the amorphous to the crystalline state. Whole-rock samples (27) and a series of successive leachates were analysed for V, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn by ICP spectrometry and for U by a delayed neutron technique. These data are supported by a variety of other mineralogical and petrographical observations. The results indicate that the metal content of the samples is predominantly inherited from the constituent detrital minerals. Reddening of the whole-rock samples does not promote major open-system migration of the heavy metals; rather, contained metals redistribute themselves on an intergranular scale, moving from detrital mineral hosts to the secondary iron oxides. The amount of secondary iron oxides and the fraction of whole-rock metals associated with these oxides increase during red-bed development. In addition, the abundance of well- crystallized iron oxides increases during this period. Differences in the leaching efficiency for various metals are related to differences in metal site distribution and intergranular permeability. Inferred conditions for rapid vs limited removal of metals from red beds are summarized. It is suggested that developed red beds which are well flushed by suitable pore fluids may be sources of significant quantities of heavy metals. -J.E.S.

Identification of light elements in silicon nitride by aberration-corrected scanning transmission electron microscopy.

PubMed

Idrobo, Juan C; Walkosz, Weronika; Klie, Robert F; Oğüt, Serdar

2012-12-01

In silicon nitride structural ceramics, the overall mechanical and thermal properties are controlled by the atomic and electronic structures at the interface between the ceramic grains and the amorphous intergranular films (IGFs) formed by various sintering additives. In the last ten years the atomic arrangements of heavy elements (rare-earths) at the Si(3)N(4)/IGF interfaces have been resolved. However, the atomic position of light elements, without which it is not possible to obtain a complete description of the interfaces, has been lacking. This review article details the authors' efforts to identify the atomic arrangement of light elements such as nitrogen and oxygen at the Si(3)N(4)/SiO(2) interface and in bulk Si(3)N(4) using aberration-corrected scanning transmission electron microscopy. Published by Elsevier B.V.

High-Temperature Stability and Grain Boundary Complexion Formation in a Nanocrystalline Cu-Zr Alloy

NASA Astrophysics Data System (ADS)

Khalajhedayati, Amirhossein; Rupert, Timothy J.

2015-12-01

Nanocrystalline Cu-3 at.% Zr powders with ~20 nm average grain size were created with mechanical alloying and their thermal stability was studied from 550-950°C. Annealing drove Zr segregation to the grain boundaries, which led to the formation of amorphous intergranular complexions at higher temperatures. Grain growth was retarded significantly, with 1 week of annealing at 950°C, or 98% of the solidus temperature, only leading to coarsening of the average grain size to 54 nm. The enhanced thermal stability can be connected to both a reduction in grain boundary energy with doping as well as the precipitation of ZrC particles. High mechanical strength is retained even after these aggressive heat treatments, showing that complexion engineering may be a viable path toward the fabrication of bulk nanostructured materials with excellent properties.

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

NASA Astrophysics Data System (ADS)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-03-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

NASA Astrophysics Data System (ADS)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-06-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

Rate-dependent behavior of the amorphous phase of spider dragline silk.

PubMed

Patil, Sandeep P; Markert, Bernd; Gräter, Frauke

2014-06-03

The time-dependent stress-strain behavior of spider dragline silk was already observed decades ago, and has been attributed to the disordered sequences in silk proteins, which compose the soft amorphous matrix. However, the actual molecular origin and magnitude of internal friction within the amorphous matrix has remained inaccessible, because experimentally decomposing the mechanical response of the amorphous matrix from the embedded crystalline units is challenging. Here, we used atomistic molecular dynamics simulations to obtain friction forces for the relative sliding of peptide chains of Araneus diadematus spider silk within bundles of these chains as a representative unit of the amorphous matrix in silk fibers. We computed the friction coefficient and coefficient of viscosity of the amorphous phase to be in the order of 10(-6) Ns/m and 10(4) Ns/m(2), respectively, by extrapolating our simulation data to the viscous limit. Finally, we used a finite element method for the amorphous phase, solely based on parameters derived from molecular dynamics simulations including the newly determined coefficient of viscosity. With this model the time scales of stress relaxation, creep, and hysteresis were assessed, and found to be in line with the macroscopic time-dependent response of silk fibers. Our results suggest the amorphous phase to be the primary source of viscosity in silk and open up the avenue for finite element method studies of silk fiber mechanics including viscous effects. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

PubMed

Mosquera-Giraldo, Laura I; Taylor, Lynne S

2015-02-02

Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

Possible existence of two amorphous phases of d-mannitol related by a first-order transition

NASA Astrophysics Data System (ADS)

Zhu, Men; Wang, Jun-Qiang; Perepezko, John H.; Yu, Lian

2015-06-01

We report that the common polyalcohol d-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature Tg (284 K), the supercooled liquid (SCL) of d-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity. On fast heating, Phase X transforms back to the SCL near Tg + 50 K, enabling a determination of their equilibrium temperature. The presence of d-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from d-mannitol's SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near Tg with substantial enthalpy decrease toward the crystalline phases; the processes in water and d-mannitol both strengthen the hydrogen bonds. In contrast to TPP, d-mannitol's Phase X forms more rapidly and can transform back to the SCL. These features make d-mannitol a valuable new model for understanding polyamorphism.

Exploiting the Phenomenon of Liquid-Liquid Phase Separation for Enhanced and Sustained Membrane Transport of a Poorly Water-Soluble Drug.

PubMed

Indulkar, Anura S; Gao, Yi; Raina, Shweta A; Zhang, Geoff G Z; Taylor, Lynne S

2016-06-06

Recent studies on aqueous supersaturated lipophilic drug solutions prepared by methods including antisolvent addition, pH swing, or dissolution of amorphous solid dispersions (ASDs) have demonstrated that when crystallization is slow, these systems undergo liquid-liquid phase separation (LLPS) when the concentration of the drug in the medium exceeds its amorphous solubility. Following LLPS, a metastable equilibrium is formed where the concentration of drug in the continuous phase corresponds to the amorphous solubility while the dispersed phase is composed of a nanosized drug-rich phase. It has been reasoned that the drug-rich phase may act as a reservoir, enabling the rate of passive transport of the drug across a membrane to be maintained at the maximum value for an extended period of time. Herein, using clotrimazole as a model drug, and a flow-through diffusion cell, the reservoir effect is demonstrated. Supersaturated clotrimazole solutions at concentrations below the amorphous solubility show a linear relationship between the maximum flux and the initial concentration. Once the concentration exceeds the amorphous solubility, the maximum flux achieved reaches a plateau. However, the duration for which the high flux persists was found to be highly dependent on the number of drug-rich nanodroplets present in the donor compartment. Macroscopic amorphous particles of clotrimazole did not lead to the same reservoir effect observed with the nanodroplets formed through the process of LLPS. A first-principles mathematical model was developed which was able to fit the experimental receiver concentration-time profiles for concentration regimes both below and above amorphous solubility, providing support for the contention that the nanodroplet phase does not directly diffuse across the membrane but, instead, rapidly replenishes the drug in the aqueous phase that has been removed by transport across the membrane. This study provides important insight into the properties of supersaturated solutions and how these might in turn impact oral absorption through effects on passive membrane transport rates.

Phase Behavior of Ritonavir Amorphous Solid Dispersions during Hydration and Dissolution.

PubMed

Purohit, Hitesh S; Taylor, Lynne S

2017-12-01

The aim of this research was to study the interplay of solid and solution state phase transformations during the dissolution of ritonavir (RTV) amorphous solid dispersions (ASDs). RTV ASDs with polyvinylpyrrolidone (PVP), polyvinylpyrrolidone vinyl acetate (PVPVA) and hydroxypropyl methylcellulose acetate succinate (HPMCAS) were prepared at 10-50% drug loading by solvent evaporation. The miscibility of RTV ASDs was studied before and after exposure to 97% relative humidity (RH). Non-sink dissolution studies were performed on fresh and moisture-exposed ASDs. RTV and polymer release were monitored using ultraviolet-visible spectroscopy. Techniques including fluorescence spectroscopy, confocal imaging, scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and nanoparticle tracking analysis (NTA) were utilized to monitor solid and the solution state phase transformations. All RTV-PVP and RTV-PVPVA ASDs underwent moisture-induced amorphous-amorphous phase separation (AAPS) on high RH storage whereas RTV-HPMCAS ASDs remained miscible. Non-sink dissolution of PVP- and PVPVA-based ASDs at low drug loadings led to rapid RTV and polymer release resulting in concentrations in excess of amorphous solubility, liquid-liquid phase separation (LLPS) and amorphous nanodroplet formation. High drug loading PVP- and PVPVA-based ASDs did not exhibit LLPS upon dissolution as a consequence of extensive AAPS in the hydrated ASD matrix. All RTV-HPMCAS ASDs led to LLPS upon dissolution. RTV ASD dissolution is governed by a competition between the dissolution rate and the rate of phase separation in the hydrated ASD matrix. LLPS was observed for ASDs where the drug release was polymer controlled and only ASDs that remained miscible during the initial phase of dissolution led to LLPS. Techniques such as fluorescence spectroscopy, confocal imaging and SEM were useful in understanding the phase behavior of ASDs upon hydration and dissolution and were helpful in elucidating the mechanism of generation of amorphous nanodroplets.

Two-phase nc-TiN/a-(C,CN{sub x}) nanocomposite films: A HRTEM and MC simulation study

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

Guo, J.; Lu, Y. H.; Hu, X. J.

2013-06-18

The grain growth in two-phase nanocomposite Ti-C{sub x}-N{sub y} thin films grown by reactive close-field unbalanced magnetron sputtering in an Ar-N{sub 2} gas mixture with microstructures comprising of nanocrystalline (nc-) Ti(N,C) phase surrounded by amorphous (a-) (C,CN{sub x}) phase was investigated by a combination of high-resolution transmission electron microscopy (HRTEM) and Monte Carlo (MC) simulations. The HRTEM results revealed that amorphous-free solid solution Ti(C,N) thin films exhibited polycrystallites with different sizes, orientations and irregular shapes. The grain size varied in the range between several nanometers and several decade nanometers. Further increase of C content (up to {approx}19 at.% C) mademore » the amorphous phase wet nanocrystallites, which strongly hindered the growth of nanocrystallites. As a result, more regular Ti(C,N) nanocrystallites with an average size of {approx}5 nm were found to be separated by {approx}0.5-nm amorphous phases. When C content was further increased (up to {approx}48 at.% in this study), thicker amorphous matrices were produced and followed by the formation of smaller sized grains with lognormal distribution. Our MC analysis indicated that with increasing amorphous volume fraction (i.e. increasing C content), the transformation from nc/nc grain boundary (GB)-curvature-driven growth to a/nc GB-curvature-driven growth is directly responsible for the observed grain growth from great inhomogeneity to homogeneity process.« less

pH-Dependent Liquid-Liquid Phase Separation of Highly Supersaturated Solutions of Weakly Basic Drugs.

PubMed

Indulkar, Anura S; Box, Karl J; Taylor, Robert; Ruiz, Rebeca; Taylor, Lynne S

2015-07-06

Supersaturated solutions of poorly aqueous soluble drugs can be formed both in vivo and in vitro. For example, increases in pH during gastrointestinal transit can decrease the aqueous solubility of weakly basic drugs resulting in supersaturation, in particular when exiting the acidic stomach environment. Recently, it has been observed that highly supersaturated solutions of drugs with low aqueous solubility can undergo liquid-liquid phase separation (LLPS) prior to crystallization, forming a turbid solution such that the concentration of the drug in the continuous solution phase corresponds to the amorphous solubility while the colloidal phase is composed of a disordered drug-rich phase. Although it is well established that the equilibrium solubility of crystalline weakly basic drugs follows the Henderson-Hasselbalch relationship, the impact of pH on the LLPS phenomenon or the amorphous solubility has not been explored. In this work, the LLPS concentration of three weakly basic compounds-clotrimazole, nicardipine, and atazanavir-was determined as a function of pH using three different methods and was compared to the predicted amorphous solubility, which was calculated from the pH-dependent crystalline solubility and by estimating the free energy difference between the amorphous and crystalline forms. It was observed that, similar to crystalline solubility, the experimental amorphous solubility at any pH follows the Henderson-Hasselbalch relation and can be predicted if the amorphous solubility of the free base is known. Excellent agreement between the LLPS concentration and the predicted amorphous solubility was observed. Dissolution studies of amorphous drugs showed that the solution concentration can reach the corresponding LLPS concentration at that pH. Solid-state analysis of the precipitated material confirmed the amorphous nature. This work provides insight into the pH-dependent precipitation behavior of poorly water-soluble compounds and provides a fundamental basis with which to understand the performance of supersaturating dosage forms.

Spontaneous crystalline-to-amorphous phase transformation of organic or medicinal compounds in the presence of porous media, part 1: thermodynamics of spontaneous amorphization.

PubMed

Qian, Ken K; Bogner, Robin H

2011-07-01

Spontaneous crystalline-to-amorphous phase transformation of organic or medicinal molecules in the presence of mesoporous materials has been observed, for which pathway was suggested to be via the vapor phase, that is, sublimation of the crystalline molecules followed by adsorption on the porous media. The objective of this paper is to rigorously evaluate this amorphization pathway and to study the thermodynamics of spontaneous amorphization. Mesoporous silicon dioxide (SiO(2)) was used as a model system. Physical mixtures of SiO(2) and crystalline compounds were prepared and stored at 0% relative humidity (RH) and 40 °C. Loss of crystallinity of the model compounds was confirmed using powder X-ray diffraction and polarized light microscopy. Adsorption chamber was set up, in which naphthalene and SiO(2) were stored, without physical contact, under reduced pressure at 0% RH and 40 °C. Data confirmed that the rate and extent of sublimation and adsorption of naphthalene were significant for amorphization to occur on a pharmaceutically relevant timescale. Furthermore, a thermodynamic model has been developed to explain spontaneous amorphization. This unique phase transformation phenomenon can be a simple and effective method to improve the aqueous solubility and bioavailability of poorly soluble drug molecules. Copyright © 2011 Wiley-Liss, Inc. and the American Pharmacists Association

Solid state amorphization of metastable Al 0.5TiZrPdCuNi high entropy alloy investigated by high voltage electron microscopy

DOE PAGES

Nagase, Takeshi; Takeuchi, Akira; Amiya, Kenji; ...

2017-07-18

Here, the phase stability of high entropy alloy (HEA), Al 0.5TiZrPdCuNi, under fast electron irradiation was studied by in-situ high voltage electron microscopy (HVEM). The initial phase of this alloy quenched from the melt was dependent on cooling rate. At high cooling rates an amorphous phase was obtained, whereas a body-centered cubic ( b.c.c.) phase were obtained at low cooling rates. By thermal crystallization of the amorphous phase b.c.c. phase nano-crystals were formed. Upon fast electron irradiation solid state amorphization (SSA) was observed in b.c.c. phase regardless of the initial microstructure (i.e., “coarse crystalline structure” or “nano-crystalline structure with grainmore » boundaries as a sink for point defects”). SSA behavior in the Al 0.5TiZrPdCuNi HEAs was investigated by in-situ transmission electron microscopy observations. Because the amorphization is very rarely achieved in a solid solution phase under fast electron irradiation in common metallic materials, this result suggests that the Al 0.5TiZrPdCuNi HEA from other common alloys and the other HEAs. The differences in phase stability against the irradiation between the Al 0.5TiZrPdCuNi HEA and the other HEAs were discussed. This is the first experimental evidence of SSA in HEAs stimulated by fast electron irradiation.« less

Exchange bias and bistable magneto-resistance states in amorphous TbFeCo thin films

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

Li, Xiaopu, E-mail: xl6ba@virginia.edu; Ma, Chung T.; Poon, S. Joseph, E-mail: sjp9x@virginia.edu

2016-01-04

Amorphous TbFeCo thin films sputter deposited at room temperature on thermally oxidized Si substrate are found to exhibit strong perpendicular magnetic anisotropy. Atom probe tomography, scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy mapping have revealed two nanoscale amorphous phases with different Tb atomic percentages distributed within the amorphous film. Exchange bias accompanied by bistable magneto-resistance states has been uncovered near room temperature by magnetization and magneto-transport measurements. The exchange anisotropy originates from the exchange interaction between the ferrimagnetic and ferromagnetic components corresponding to the two amorphous phases. This study provides a platform for exchange bias and magneto-resistance switchingmore » using single-layer amorphous ferrimagnetic thin films that require no epitaxial growth.« less

X-ray diffraction investigation of amorphous calcium phosphate and hydroxyapatite under ultra-high hydrostatic pressure

NASA Astrophysics Data System (ADS)

Lam, Elisa; Gu, Qinfen; Swedlund, Peter J.; Marchesseau, Sylvie; Hemar, Yacine

2015-11-01

The changes in the crystal structures of synthetically prepared amorphous calcium phosphate (ACP) and hydroxyapatite (HAP) in water (1:1 mass ratio) were studied by synchrotron X-ray diffraction (XRD) under ultra-high hydrostatic pressures as high as 2.34 GPa for ACP and 4 GPa for HAP. At ambient pressure, the XRD patterns of the ACP and HAP samples in capillary tubes and their environmental scanning electron micrographs indicated amorphous and crystalline characteristics for ACP and HAP, respectively. At pressures greater than 0.25 GPa, an additional broad peak was observed in the XRD pattern of the ACP phase, indicating a partial phase transition from an amorphous phase to a new high-pressure amorphous phase. The peak areas and positions of the ACP phase, as obtained through fitting of the experimental data, indicated that the ACP exhibited increased pseudo-crystalline behavior at pressures greater than 0.96 GPa. Conversely, no structural changes were observed for the HAP phase up to the highest applied pressure of 4 GPa. For HAP, a unit-cell reduction during compression was evidenced by a reduction in both refined lattice parameters a and c. Both ACP and HAP reverted to their original structures when the pressure was fully released to ambient pressure.

Addressing the amorphous content issue in quantitative phase analysis : the certification of NIST SRM 676a.

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

Cline, J. P.; Von Dreele, R. B.; Winburn, R.

2011-07-01

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Undermore » the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.« less

Addressing the Amorphous Content Issue in Quantitative Phase Analysis: The Certification of NIST Standard Reference Material 676a

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

J Cline; R Von Dreele; R Winburn

2011-12-31

A non-diffracting surface layer exists at any boundary of a crystal and can comprise a mass fraction of several percent in a finely divided solid. This has led to the long-standing issue of amorphous content in standards for quantitative phase analysis (QPA). NIST standard reference material (SRM) 676a is a corundum ({alpha}-Al{sub 2}O{sub 3}) powder, certified with respect to phase purity for use as an internal standard in powder diffraction QPA. The amorphous content of SRM 676a is determined by comparing diffraction data from mixtures with samples of silicon powders that were engineered to vary their specific surface area. Undermore » the (supported) assumption that the thickness of an amorphous surface layer on Si was invariant, this provided a method to control the crystalline/amorphous ratio of the silicon components of 50/50 weight mixtures of SRM 676a with silicon. Powder diffraction experiments utilizing neutron time-of-flight and 25 keV and 67 keV X-ray energies quantified the crystalline phase fractions from a series of specimens. Results from Rietveld analyses, which included a model for extinction effects in the silicon, of these data were extrapolated to the limit of zero amorphous content of the Si powder. The certified phase purity of SRM 676a is 99.02% {+-} 1.11% (95% confidence interval). This novel certification method permits quantification of amorphous content for any sample of interest, by spiking with SRM 676a.« less

Structure-composition-property relationships in 5xxx series aluminum alloys

NASA Astrophysics Data System (ADS)

Unocic, Kinga A.

Al-Mg alloys are well suited for marine applications due to their low density, ease of fabrication, structural durability, and most notably resistance to corrosion. The purpose of this study is to investigate the effects of alloying additions, mechanical processing and heat treatments on the development of grain boundary phases that have an effect on intergranular corrosion (IGC). Cu, Zn, and Si modified compositions of AA5083 were produced that were subjected to a low and high degree of cold work and various heat treatments. ASTM G67 (NAMLT) intergranular corrosion testing and detailed microstructural characterization for various alloys was carried out. An optimal composition and processing condition that yielded the best intergranular corrosion resistant material was identified based on the ASTM G67 test screening. Further, the outstanding modified AA5083 was selected for further microstructural analysis. This particular alloy with has a magnesium level high enough to make it susceptible to intergranular corrosion is very resistant to IGC. It was found that development of the appropriate sub-structure with some Cu, Si and Zn resulted in a material very resistant to IGC. Formation of many sinks, provided by sub-boundaries, within microstructure is very beneficial since it produces a relatively uniform distribution of Mg in the grain interiors, and this can suppress sensitization of this alloy very successfully. This is a very promising rote for the production of high-strength, and corrosion resistant aluminum alloys. Additionally in this study, TEM sample preparation become very crucial step in grain boundary phase investigation. Focus Ion Beam (FIB) milling was used as a primary TEM sample preparation technique because it enables to extract the samples from desired and very specific locations without dissolving grain boundary phases as it was in conventional electropolishing method. However, other issues specifically relevant to FIB milling of aluminum alloys related to Ga accumulation were discovered, that produce significant microstructural artifacts. It is well known that liquid gallium can cause Liquid Metal Embitterment (LME) aluminum alloys, and gallium readily penetrates aluminum grain boundaries. Low energy Ar ion nanomilling is potentially quite effective at removing gallium from the external and internal surfaces of aluminum thin foils, but can still leave persistent artifacts. Al-Mg alloys can be also susceptible to localized corrosion such as pitting corrosion in the presence of chloride ions. In this study the phases responsible for this type of corrosion were identified. ASSET (ASTM G66) test was used to determine the influence of heat-treatment on pitting corrosion on various modified AA5083 alloys. Additionally, potentiodynamic polarization as well as potentiostatic measurements in conjunction with SEM analysis were carried out to obtain pitting potential (Epit) and to determine the location of metastable pit initiation, respectively.

Femtosecond laser-induced phase transformations in amorphous Cu77Ni6Sn10P7 alloy

NASA Astrophysics Data System (ADS)

Zhang, Y.; Liu, L.; Zou, G.; Chen, N.; Wu, A.; Bai, H.; Zhou, Y.

2015-01-01

In this study, the femtosecond laser-induced crystallization of CuNiSnP amorphous ribbons was investigated by utilizing an amplified Ti:sapphire laser system. X-ray diffraction and scanning electronic microscope were applied to examine the phase and morphology changes of the amorphous ribbons. Micromachining without crystallization, surface patterning, and selective crystallization were successfully achieved by changing laser parameters. Obvious crystallization occurred under the condition that the laser fluence was smaller than the ablation threshold, indicating that the structural evolution of the material depends strongly on the laser parameters. Back cooling method was used to inhibit heat accumulation; a reversible transformation between the disordered amorphous and crystalline phases can be achieved by using this method.

Transformation of amorphous TiO 2 to a hydronium oxofluorotitanate and applications as an HF sensor

DOE PAGES

Appelhans, Leah N.; Finnegan, Patrick S.; Massey, Lee T.; ...

2015-12-24

We examined amorphous titania thin films for use as the active material in a polarimetry based HF sensor. The amorphous titania films were found to be sensitive to vapor phase HF and the reaction product was identified as a hydronium oxofluorotitanate phase, which has previously only been synthesized in aqueous solution. The extent of reaction varied both with vapor phase HF concentration, relative humidity, and the exposure time. HF concentrations as low as 1 ppm could be detected for exposure times of 120 h.

Effects of In Situ Intermetallics on the Microstructural Array and Saline Corrosion Performance of Cast Al/WCp Composites

NASA Astrophysics Data System (ADS)

Lekatou, A. G.; Gkikas, N.; Gousia, V.; Lentzaris, K.; Karantzalis, A. E.

2018-06-01

Al-matrix composites, ex situ reinforced with WC nanoparticles and in situ reinforced with Al3(Ti,W), Al12W, Al5W and Al4W, have been fabricated by casting assisted by K2TiF6 wetting agent addition and mechanical stirring. A satisfactory particle incorporation and distribution accompanied by a high reactivity have been attained. The presence, topography, chemical composition of all included phases and their occurrence as clusters or single particles are clarified and justified. Al12W is the predominant aluminide phase at WC ≤ 1.5 vol.%. Al4W (primarily) and Al5W (secondarily) are the predominant aluminide phases at WC ≥ 2.0 vol.%. WC nanoparticles have acted as heterogeneous nucleation sites to Al3Ti particles. Reverse polarization tests in 3.5 wt.% NaCl show that the governing form of corrosion is intergranular corrosion of Al around Al3FeSi2 eutectic, fine plates. The corrosion steps/mechanisms are identified. Clusters of aluminides and carbide nanoparticles, as well as intergranular WC nano-dispersoids and their Al-matrix have remained corrosion-free. The role of the aluminides combined with WC remaining nano-cores as inhibitors of the eutectic Al3FeSi2 cathodic activity is highlighted.

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

Yi, Gaosong; Cullen, David A.; Littrell, Kenneth C.

For this research, long-term aged [343 K (70 °C) for 30 months and natural exposure for over 10 years] Al 5456 H116 samples were characterized using electron backscatter diffraction (EBSD), scanning transmission electron microscopy (STEM), state-of-the-art energy-dispersive X-ray spectroscopy (EDS) systems, and small-angle neutron scattering (SANS). ASTM G-67 mass loss tests of the sensitized Al 5456 alloy samples were conducted. Intragranular Mg-rich precipitates, such as Guinier–Preston (GP) zones, were confirmed in Al 5456 H116 aged at 343 K (70 °C) for 30 months, and the volume of these precipitates is 1.39 pct. β' phase is identified at the grain boundarymore » of a navy ship sample, while high-resolution STEM results reveal no intragranular precipitates. Intergranular corrosion (IGC) of Al 5456 was found to be related to the continuity of intergranular precipitates.« less

Formation of an amorphous phase and its crystallization in the immiscible Nb-Zr system by mechanical alloying

NASA Astrophysics Data System (ADS)

Al-Aqeeli, N.; Suryanarayana, C.; Hussein, M. A.

2013-10-01

Mechanical alloying of binary Nb-Zr powder mixtures was carried out to evaluate the formation of metastable phases in this immiscible system. The milled powders were characterized for their constitution and structure by X-ray diffraction and transmission electron microscopy methods. It was shown that an amorphous phase had formed on milling the binary powder mixture for about 10 h and that it had crystallized on subsequent milling up to 50-70 h, referred to as mechanical crystallization. Thermodynamic and structural arguments have been presented to explain the formation of the amorphous phase and its subsequent crystallization.

Possible existence of two amorphous phases of D-mannitol related by a first-order transition

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

Zhu, Men; Yu, Lian, E-mail: lian.yu@wisc.edu; Wang, Jun-Qiang

2015-06-28

We report that the common polyalcohol D-mannitol may have two amorphous phases related by a first-order transition. Slightly above its glass transition temperature T{sub g} (284 K), the supercooled liquid (SCL) of D-mannitol transforms to a low-energy, apparently amorphous phase with stronger hydrogen bonds. The enthalpy of this so-called Phase X is approximately halfway between those of the known amorphous and crystalline phases, a position low for glass aging and high for crystal polymorphs. Similar to the SCL, Phase X is transparent with broad X-ray diffraction and Raman scattering; upon temperature cycling, it exhibits a glass-transition-like change of heat capacity.more » On fast heating, Phase X transforms back to the SCL near T{sub g} + 50 K, enabling a determination of their equilibrium temperature. The presence of D-sorbitol as a plasticizer enables observation of a first-order transition from the SCL to Phase X entirely in the liquid state (liquid-liquid transition). The transition from D-mannitol’s SCL to Phase X has intriguing similarities with the formation of the glacial phase of triphenyl phosphite (TPP) and the conversion from high-density to low-density amorphous ice, both studied intensely in the context of polyamorphism. All three processes occur near T{sub g} with substantial enthalpy decrease toward the crystalline phases; the processes in water and D-mannitol both strengthen the hydrogen bonds. In contrast to TPP, D-mannitol’s Phase X forms more rapidly and can transform back to the SCL. These features make D-mannitol a valuable new model for understanding polyamorphism.« less

Influence of the exchange and correlation functional on the structure of amorphous InSb and In3SbTe2 compounds

NASA Astrophysics Data System (ADS)

Gabardi, Silvia; Caravati, Sebastiano; Los, Jan H.; Kühne, Thomas D.; Bernasconi, Marco

2016-05-01

We have investigated the structural, vibrational, and electronic properties of the amorphous phase of InSb and In3SbTe2 compounds of interest for applications in phase change non-volatile memories. Models of the amorphous phase have been generated by quenching from the melt by molecular dynamics simulations based on density functional theory. In particular, we have studied the dependence of the structural properties on the choice of the exchange-correlation functional. It turns out that the use of the Becke-Lee-Yang-Parr functional provides models with a much larger fraction of In atoms in a tetrahedral bonding geometry with respect to previous results obtained with the most commonly used Perdew-Becke-Ernzerhof functional. This outcome is at odd with the properties of Ge2Sb2Te5 phase change compound for which the two exchange-correlation functionals yield very similar results on the structure of the amorphous phase.

Influence of the exchange and correlation functional on the structure of amorphous InSb and In3SbTe2 compounds.

PubMed

Gabardi, Silvia; Caravati, Sebastiano; Los, Jan H; Kühne, Thomas D; Bernasconi, Marco

2016-05-28

We have investigated the structural, vibrational, and electronic properties of the amorphous phase of InSb and In3SbTe2 compounds of interest for applications in phase change non-volatile memories. Models of the amorphous phase have been generated by quenching from the melt by molecular dynamics simulations based on density functional theory. In particular, we have studied the dependence of the structural properties on the choice of the exchange-correlation functional. It turns out that the use of the Becke-Lee-Yang-Parr functional provides models with a much larger fraction of In atoms in a tetrahedral bonding geometry with respect to previous results obtained with the most commonly used Perdew-Becke-Ernzerhof functional. This outcome is at odd with the properties of Ge2Sb2Te5 phase change compound for which the two exchange-correlation functionals yield very similar results on the structure of the amorphous phase.

Electron microscopy observation of TiO2 nanocrystal evolution in high-temperature atomic layer deposition.

PubMed

Shi, Jian; Li, Zhaodong; Kvit, Alexander; Krylyuk, Sergiy; Davydov, Albert V; Wang, Xudong

2013-01-01

Understanding the evolution of amorphous and crystalline phases during atomic layer deposition (ALD) is essential for creating high quality dielectrics, multifunctional films/coatings, and predictable surface functionalization. Through comprehensive atomistic electron microscopy study of ALD TiO2 nanostructures at designed growth cycles, we revealed the transformation process and sequence of atom arrangement during TiO2 ALD growth. Evolution of TiO2 nanostructures in ALD was found following a path from amorphous layers to amorphous particles to metastable crystallites and ultimately to stable crystalline forms. Such a phase evolution is a manifestation of the Ostwald-Lussac Law, which governs the advent sequence and amount ratio of different phases in high-temperature TiO2 ALD nanostructures. The amorphous-crystalline mixture also enables a unique anisotropic crystal growth behavior at high temperature forming TiO2 nanorods via the principle of vapor-phase oriented attachment.

MC3T3-E1 cell response of amorphous phase/TiO2 nanocrystal composite coating prepared by microarc oxidation on titanium.

PubMed

Zhou, Rui; Wei, Daqing; Yang, Haoyue; Feng, Wei; Cheng, Su; Li, Baoqiang; Wang, Yaming; Jia, Dechang; Zhou, Yu

2014-06-01

Bioactive amorphous phase/TiO2 nanocrystal (APTN) composite coatings were fabricated by microarc oxidation (MAO) on Ti. The APTN coatings are composed of much amorphous phase with Si, Na, Ca, Ti and O elements and a few TiO2 nanocrystals. With increasing applied voltage, the micropore density of the APTN coating decreases and the micropore size of the APTN coating increases. The results indicate that less MC3T3-E1 cells attach on the APTN coatings as compared to Ti. However, the APTN coatings greatly enhance the cell proliferation ability and the activity of alkaline phosphatase. The amorphous phase and the concentrations of the released Ca and Si from the APTN coatings during cell culture have significant effects on the cell response. Copyright © 2014 Elsevier B.V. All rights reserved.

Phase transitions in biogenic amorphous calcium carbonate.

PubMed

Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

2012-04-17

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.

Phase transitions in biogenic amorphous calcium carbonate

PubMed Central

Gong, Yutao U. T.; Killian, Christopher E.; Olson, Ian C.; Appathurai, Narayana P.; Amasino, Audra L.; Martin, Michael C.; Holt, Liam J.; Wilt, Fred H.; Gilbert, P. U. P. A.

2012-01-01

Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H2O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H2O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H2O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H2O in vitro. PMID:22492931

Role of composition, bond covalency, and short-range order in the disordering of stannate pyrochlores by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Shamblin, Jacob; Park, Sulgiye; Zhang, Fuxiang; Trautmann, Christina; Lang, Maik; Ewing, Rodney C.

2016-08-01

A2S n2O7 (A =Nd ,Sm,Gd,Er,Yb,and Y) materials with the pyrochlore structure were irradiated with 2.2 GeV Au ions to systematically investigate disordering of this system in response to dense electronic excitation. Structural modifications were characterized, over multiple length scales, by transmission electron microscopy, x-ray diffraction, and Raman spectroscopy. Transformations to amorphous and disordered phases were observed, with disordering dominating the structural response of materials with small A -site cation ionic radii. Both the disordered and amorphous phases were found to possess weberite-type local ordering, differing only in that the disordered phase exhibits a long-range, modulated arrangement of weberite-type structural units into an average defect-fluorite structure, while the amorphous phase remains fully aperiodic. Comparison with the behavior of titanate and zirconate pyrochlores showed minimal influence of the high covalency of the Sn-O bond on this phase behavior. An analytical model of damage accumulation was developed to account for simultaneous amorphization and recrystallization of the disordered phase during irradiation.

Investigation of crystalline morphology in poly (ether ether ketone) using dielectric relaxation spectroscopy

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

Kalika, D.S.; Krishnaswamy, R.K.

1993-12-31

The relaxation behavior of poly (ether ether ketone) [PEEK] has been investigated using dielectric relaxation spectroscopy; the glass-rubber ({alpha}) relaxation and a sub-glass ({beta}) relaxation were examined for the amorphous material and both cold-crystallized and melt-crystallized specimens. Analysis of the data using the Cole-Cole modification of the Debye equation allowed determination of the dielectric relaxation strength and relaxation broadening parameter for both transitions as a function of material crystallization history. The crystallized specimens displayed a positive offset in isochronal loss temperature for both the {alpha} and {beta} relaxations, with the {alpha} relaxation broadened significantly. The measured dipolar response was interpretedmore » using a three-phase morphological model encompassing a crystalline phase, a mobile amorphous phase, and a rigid amorphous phase. Determination of phase fractions based on dipolar mobilization across the glass-rubber relaxation revealed a finite rigid amorphous phase fraction for both the cold-crystallized specimens which was relatively insensitive to thermal history and degree of crystallinity (W{sub RAP}40.20).« less

Phase separation and crystallization process of amorphous Fe{sub 78}B{sub 12}Si{sub 9}Ni{sub 1} alloy

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

Mukhgalin, V. V.; Lad’yanov, V. I.

2015-08-17

The influence of the melt heat treatment on the structure and crystallization process of the rapidly quenched amorphous Fe{sub 78}B{sub 12}Si{sub 9}Ni{sub 1} alloys have been investigated by means of x-ray diffraction, DSC and TEM. Amorphous phase separation has been observed in the alloys quenched after the preliminary high temperature heat treatment of the liquid alloy (heating above 1400°C). Comparative analysis of the pair distribution functions demonstrates that this phase separation accompanied by a changes in the local atomic arrangement. It has been found that crystallization process at heating is strongly dependent on the initial amorphous phase structure - homogeneousmore » or phase separated. In the last case crystallization goes through the formation of a new metastable hexagonal phase [a=12.2849(9) Ǻ, c=7.6657(8) Ǻ]. At the same time the activation energy for crystallization (Ea) reduces from 555 to 475 kJ mole{sup −1}.« less

Aging mechanisms in amorphous phase-change materials.

PubMed

Raty, Jean Yves; Zhang, Wei; Luckas, Jennifer; Chen, Chao; Mazzarello, Riccardo; Bichara, Christophe; Wuttig, Matthias

2015-06-24

Aging is a ubiquitous phenomenon in glasses. In the case of phase-change materials, it leads to a drift in the electrical resistance, which hinders the development of ultrahigh density storage devices. Here we elucidate the aging process in amorphous GeTe, a prototypical phase-change material, by advanced numerical simulations, photothermal deflection spectroscopy and impedance spectroscopy experiments. We show that aging is accompanied by a progressive change of the local chemical order towards the crystalline one. Yet, the glass evolves towards a covalent amorphous network with increasing Peierls distortion, whose structural and electronic properties drift away from those of the resonantly bonded crystal. This behaviour sets phase-change materials apart from conventional glass-forming systems, which display the same local structure and bonding in both phases.

Amorphous Analogs of Martian Global Soil: Pair Distribution Function Analyses and Implications for Scattering Models of Chemin X-ray Diffraction Data

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Bish, D. L.; Rampe, E. B.; Morris, R. V.

2015-01-01

Soils on Mars have been analyzed by the Mars Exploration Rovers (MER) and most recently by the Mars Science Laboratory (MSL) rover. Chemical analyses from a majority of soil samples suggest that there is a relatively uniform global soil composition across much of the planet. A soil site, Rocknest, was sampled by the MSL science payload including the CheMin X-ray diffractometer and the Alpha Particle X-ray Spectrometer (APXS). Che- Min X-ray diffraction (XRD) data revealed crystalline phases and a broad, elevated background, indicating the presence of amorphous or poorly ordered materials (Fig 1). Based on the chemical composition of the bulk soil measured by APXS and the composition of crystalline phases derived from unit-cell parameters determined with CheMin data, the percentages of crystalline and amorphous phases were calculated at 51% and 49%, respectively. Attempts to model the amorphous contribution to CheMin XRD patterns were made using amorphous standards and full-pattern fitting methods and show that the broad, elevated background region can be fitted by basaltic glass, allophane, and palagonite. However, the modeling shows only that these phases have scattering patterns similar to that for the soil, not that they represent unique solutions. Here, we use pair distribution function (PDF) analysis to determine the short-range order of amorphous analogs in martian soils and better constrain the amorphous material detected by CheMin.

Hydration products in sulfoaluminate cements: Evaluation of amorphous phases by XRD/solid-state NMR

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

Gastaldi, D., E-mail: dgastaldi@buzziunicem.it; Paul, G., E-mail: geo.paul@uniupo.it; Marchese, L.

The hydration of four sulfoaluminate cements have been studied: three sulfoaluminate systems, having different content of sulfate and silicate, and one blend Portland-CSA-calcium sulfate binder. Hydration was followed up to 90 days by means of a combination of X-ray diffraction and solid state MAS-NMR; Differential scanning calorimetry and Scanning electron microscopy were also performed in order to help the interpretation of experimental data. High amount of amorphous phases were found in all the four systems: in low-sulfate cements, amorphous part is mainly ascribed to monosulfate and aluminium hydroxide, while strätlingite is observed if belite is present in the cement; inmore » the blend system, C-S-H contributes to the amorphous phase beyond monosulfate.« less

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

PubMed

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

Unique Bond Breaking in Crystalline Phase Change Materials and the Quest for Metavalent Bonding.

PubMed

Zhu, Min; Cojocaru-Mirédin, Oana; Mio, Antonio M; Keutgen, Jens; Küpers, Michael; Yu, Yuan; Cho, Ju-Young; Dronskowski, Richard; Wuttig, Matthias

2018-05-01

Laser-assisted field evaporation is studied in a large number of compounds, including amorphous and crystalline phase change materials employing atom probe tomography. This study reveals significant differences in field evaporation between amorphous and crystalline phase change materials. High probabilities for multiple events with more than a single ion detected per laser pulse are only found for crystalline phase change materials. The specifics of this unusual field evaporation are unlike any other mechanism shown previously to lead to high probabilities of multiple events. On the contrary, amorphous phase change materials as well as other covalently bonded compounds and metals possess much lower probabilities for multiple events. Hence, laser-assisted field evaporation in amorphous and crystalline phase change materials reveals striking differences in bond rupture. This is indicative for pronounced differences in bonding. These findings imply that the bonding mechanism in crystalline phase change materials differs substantially from conventional bonding mechanisms such as metallic, ionic, and covalent bonding. Instead, the data reported here confirm a recently developed conjecture, namely that metavalent bonding is a novel bonding mechanism besides those mentioned previously. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomistic insights into the nanosecond long amorphization and crystallization cycle of nanoscale G e2S b2T e5 : An ab initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Branicio, Paulo S.; Bai, Kewu; Ramanarayan, H.; Wu, David T.; Sullivan, Michael B.; Srolovitz, David J.

2018-04-01

The complete process of amorphization and crystallization of the phase-change material G e2S b2T e5 is investigated using nanosecond ab initio molecular dynamics simulations. Varying the quench rate during the amorphization phase of the cycle results in the generation of a variety of structures from entirely crystallized (-0.45 K/ps) to entirely amorphized (-16 K/ps). The 1.5-ns annealing simulations indicate that the crystallization process depends strongly on both the annealing temperature and the initial amorphous structure. The presence of crystal precursors (square rings) in the amorphous matrix enhances nucleation/crystallization kinetics. The simulation data are used to construct a combined continuous-cooling-transformation (CCT) and temperature-time-transformation (TTT) diagram. The nose of the CCT-TTT diagram corresponds to the minimum time for the onset of homogenous crystallization and is located at 600 K and 70 ps. That corresponds to a critical cooling rate for amorphization of -4.5 K/ps. The results, in excellent agreement with experimental observations, suggest that a strategy that utilizes multiple quench rates and annealing temperatures may be used to effectively optimize the reversible switching speed and enable fast and energy-efficient phase-change memories.

Role of mechanical stress in the resistance drift of Ge2Sb2Te5 films and phase change memories

NASA Astrophysics Data System (ADS)

Rizzi, M.; Spessot, A.; Fantini, P.; Ielmini, D.

2011-11-01

In a phase change memory (PCM), the device resistance increases slowly with time after the formation of the amorphous phase, thus affecting the stability of stored data. This work investigates the resistance drift in thin films of amorphous Ge2Sb2Te5 and in PCMs, demonstrating a common kinetic of drift in stressed/unstressed films and in the nanometer-size active volume of a PCM with different stress levels developed via stressor layers. It is concluded that stress is not the root cause of PCM drift, which is instead attributed to intrinsic structural relaxation due to the disordered, metastable nature of the amorphous chalcogenide phase.

Role of electronic excitation in the amorphization of Ge-Sb-Te alloys.

PubMed

Li, Xian-Bin; Liu, X Q; Liu, Xin; Han, Dong; Zhang, Z; Han, X D; Sun, Hong-Bo; Zhang, S B

2011-07-01

First-principles molecular dynamics simulation reveals the effects of electronic excitation in the amorphization of Ge-Sb-Te. The excitation makes the phase change an element-selective process, lowers the critical amorphization temperature considerably, for example, to below 700 K at a 9% excitation, and reduces the atomic diffusion coefficient with respect to that of melt by at least 1 order of magnitude. Noticeably, the resulting structure has fewer wrong bonds and significantly increased phase-change reversibility. Our results point to a new direction in manipulating ultrafast phase-change processes with improved controllability.

Molybdenum Carbamate Nanosheets as a New Class of Potential Phase Change Materials.

PubMed

Zhukovskyi, Maksym; Plashnitsa, Vladimir; Petchsang, Nattasamon; Ruth, Anthony; Bajpai, Anshumaan; Vietmeyer, Felix; Wang, Yuanxing; Brennan, Michael; Pang, Yunsong; Werellapatha, Kalpani; Bunker, Bruce; Chattopadhyay, Soma; Luo, Tengfei; Janko, Boldizsar; Fay, Patrick; Kuno, Masaru

2017-06-14

We report for the first time the synthesis of large, free-standing, Mo 2 O 2 (μ-S) 2 (Et 2 dtc) 2 (MoDTC) nanosheets (NSs), which exhibit an electron-beam induced crystalline-to-amorphous phase transition. Both electron beam ionization and femtosecond (fs) optical excitation induce the phase transition, which is size-, morphology-, and composition-preserving. Resulting NSs are the largest, free-standing regularly shaped two-dimensional amorphous nanostructures made to date. More importantly, amorphization is accompanied by dramatic changes to the NS electrical and optical response wherein resulting amorphous species exhibit room-temperature conductivities 5 orders of magnitude larger than those of their crystalline counterparts. This enhancement likely stems from the amorphization-induced formation of sulfur vacancy-related defects and is supported by temperature-dependent transport measurements, which reveal efficient variable range hopping. MoDTC NSs represent one instance of a broader class of transition metal carbamates likely having applications because of their intriguing electrical properties as well as demonstrated ability to toggle metal oxidation states.

Thermodynamically controlled crystallization of glucose pentaacetates from amorphous phase

NASA Astrophysics Data System (ADS)

Wlodarczyk, P.; Hawelek, L.; Hudecki, A.; Wlodarczyk, A.; Kolano-Burian, A.

2016-08-01

The α and β glucose pentaacetates are known sugar derivatives, which can be potentially used as stabilizers of amorphous phase of active ingredients of drugs (API). In the present work, crystallization behavior of equimolar mixture of α and β form in comparison to both pure anomers is revealed. It was shown that despite the same molecular interactions and similar molecular dynamics, crystallization from amorphous phase is significantly suppressed in equimolar mixture. Time dependent X-ray diffraction studies confirmed higher stability of the quenched amorphous equimolar mixture. Its tendency to crystallization is about 10 times lower than for pure anomers. Calorimetric studies revealed that the α and β anomers don't form solid solutions and have eutectic point for xα = 0.625. Suppressed crystallization tendency in the mixture is probably caused by the altered thermodynamics of the system. The factors such as difference of free energy between crystalline and amorphous state or altered configurational entropy are probably responsible for the inhibitory effect.

Thermodynamically controlled crystallization of glucose pentaacetates from amorphous phase

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

Wlodarczyk, P., E-mail: patrykw@imn.gliwice.pl; Hawelek, L.; Hudecki, A.

The α and β glucose pentaacetates are known sugar derivatives, which can be potentially used as stabilizers of amorphous phase of active ingredients of drugs (API). In the present work, crystallization behavior of equimolar mixture of α and β form in comparison to both pure anomers is revealed. It was shown that despite the same molecular interactions and similar molecular dynamics, crystallization from amorphous phase is significantly suppressed in equimolar mixture. Time dependent X-ray diffraction studies confirmed higher stability of the quenched amorphous equimolar mixture. Its tendency to crystallization is about 10 times lower than for pure anomers. Calorimetric studiesmore » revealed that the α and β anomers don’t form solid solutions and have eutectic point for x{sub α} = 0.625. Suppressed crystallization tendency in the mixture is probably caused by the altered thermodynamics of the system. The factors such as difference of free energy between crystalline and amorphous state or altered configurational entropy are probably responsible for the inhibitory effect.« less

Thermodynamic analysis and purifying an amorphous phase of frozen crystallization centers

NASA Astrophysics Data System (ADS)

Lysov, V. I.; Tsaregradskaya, T. L.; Turkov, O. V.; Saenko, G. V.

2017-12-01

The possibility of dissolving frozen crystallization centers in amorphous alloys of the Fe-B system is considered by means of thermodynamic calculations. This can in turn improve the thermal stability of an amorphous alloy. The effect isothermal annealing has on the thermal stability of multicomponent amorphous alloys based on iron is investigated via the highly sensitive dilatometric technique, measurements of microsolidity, and electron microscopic investigations. The annealing temperature is determined empirically on the basis of the theses of the thermodynamic theory of the high temperature stability of multicomponent amorphous alloys, according to which there exists a range of temperatures that is characterized by a negative difference between the chemical potentials of phases in a heterogeneous amorphous matrix-frozen crystallization centers system. The thermodynamic condition of the possible dissolution of frozen crystallization centers is thus met. It is shown that introducing regimes of thermal processing allows us to expand the ranges of the thermal stability of iron-based amorphous alloys by 20-40 K through purifying an amorphous matrix of frozen crystallization centers. This conclusion is proved via electron microscopic investigations.

Self Exchange Bias and Bi-stable Magneto-Resistance States in Amorphous TbFeCo and TbSmFeCo Thin Films

NASA Astrophysics Data System (ADS)

Ma, Chung; Li, Xiaopu; Lu, Jiwei; Poon, Joseph; Comes, Ryan; Devaraj, Arun; Spurgeon, Steven

Amorphous ferrimagetic TbFeCo and TbSmFeCo thin films are found to exhibit strong perpendicular magnetic anisotropy. Self exchange bias effect and bi-stable magneto-resistance states are observed near compensation temperature by magnetic hysteresis loop, anomalous Hall effect and transverse magneto-resistance measurements. Atom probe tomography, scanning transmission electron microscopy, and energy dispersive spectroscopy mapping have revealed two nanoscale amorphous phases with different Tb concentration distributed within the amorphous films. The observed exchange anisotropy originates from the exchange interaction between the two nanoscale amorphous phases. Exchange bias effect is used for increasing stability in spin valves and magnetic tunneling junctions. This study opens up a new platform for using amorphous ferrimagnetic thin films that require no epitaxial growth in nanodevices.. The work was supported by the Defense Threat Reduction Agency Grant and the U.S. Department of Energy.

Switching of the direction of reflectionless light propagation at exceptional points in non-PT-symmetric structures using phase-change materials.

PubMed

Huang, Yin; Shen, Yuecheng; Min, Changjun; Veronis, Georgios

2017-10-30

We introduce a non-parity-time-symmetric three-layer structure, consisting of a gain medium layer sandwiched between two phase-change medium layers for switching of the direction of reflectionless light propagation. We show that for this structure unidirectional reflectionlessness in the forward direction can be switched to unidirectional reflectionlessness in the backward direction at the optical communication wavelength by switching the phase-change material Ge 2 Sb 2 Te 5 (GST) from its amorphous to its crystalline phase. We also show that it is the existence of exceptional points for this structure with GST in both its amorphous and crystalline phases which leads to unidirectional reflectionless propagation in the forward direction for GST in its amorphous phase, and in the backward direction for GST in its crystalline phase. Our results could be potentially important for developing a new generation of compact active free-space optical devices.

Intergranular stress corrosion cracking and selective internal oxidation of nickel-chromium-iron alloys in hydrogenated steam

NASA Astrophysics Data System (ADS)

Capell, Brent M.

2005-07-01

Selective internal oxidation (SIO) is a mechanism of grain boundary embrittlement through the formation of intergranular oxides of Cr2O3. SIO is proposed as a mechanism to explain intergranular stress corrosion cracking (IGSCC) of Ni-base alloys in pressurized water reactor environments. The purpose of this work is to investigate SIO through a series of experiments using controlled-purity alloys in a controlled, low-pressure steam environment in which the oxygen potential is varied. Five alloys; Ni-9Fe, Ni-5Cr, LCr (Ni-5Cr-9Fe), CD85 (Ni-16Cr-9Fe) and HCr (Ni-30Cr-9Fe), were used in corrosion coupon exposure tests and constant extension rate tensile (CERT) tests at 550°C and 400°C in an environment consisting of a controlled mixture of hydrogen, water vapor and argon. The hydrogen-to-water vapor partial pressure ratio (PPR) was varied between 0.001 and 0.9 to control the oxygen partial pressure. The Ni-9Fe, Ni-5Cr and LCr alloys formed a uniform Ni(OH)2 film at PPR values less than 0.09 while CD85 and HCr formed Cr2O 3 oxide films over the entire PPR range. Corrosion coupon results also show the formation of highly localized oxide particles at grain boundaries. Focused ion beam analysis revealed that intergranular oxides were observed at significant depths (>150 nm) down grain boundaries and the oxide morphology depended on the alloy composition and PPR value. Diffusion of oxygen along the grain boundary accounted for the growth of intergranular oxides. CERT test results showed that intergranular cracking was caused by creep-induced microvoid coalescence only at 550°C and did not depend on PPR. At 400°C, the cracking behavior depended on the PPR and resulted in a mixture of creep-induced microvoid coalescence and brittle intergranular failure. The cracked boundary fraction was higher at a PPR value where a Ni(OH)2 surface film formed. Alloy composition influenced cracking and the cracked boundary fraction decreased as the alloy chromium content increased. The compositions of oxides at intergranular crack tips were similar to intergranular oxides in corrosion coupons and demonstrated a link between intergranular oxide formation and intergranular cracking. The observation of intergranular oxides as well as the influence of alloy content on IG cracking was found to support SIO as a mechanism for IGSCC.

Competing covalent and ionic bonding in Ge-Sb-Te phase change materials

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

Subedi, Alaska; Siegrist, Theo; Singh, David J.

Ge 2Sb 2Te 5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strongmore » competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO 3, BiFeO 3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. As a result, this different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.« less

Competing covalent and ionic bonding in Ge-Sb-Te phase change materials

DOE PAGES

Subedi, Alaska; Siegrist, Theo; Singh, David J.; ...

2016-05-19

Ge 2Sb 2Te 5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strongmore » competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO 3, BiFeO 3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. As a result, this different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.« less

Competing covalent and ionic bonding in Ge-Sb-Te phase change materials.

PubMed

Mukhopadhyay, Saikat; Sun, Jifeng; Subedi, Alaska; Siegrist, Theo; Singh, David J

2016-05-19

Ge2Sb2Te5 and related phase change materials are highly unusual in that they can be readily transformed between amorphous and crystalline states using very fast melt, quench, anneal cycles, although the resulting states are extremely long lived at ambient temperature. These states have remarkably different physical properties including very different optical constants in the visible in strong contrast to common glass formers such as silicates or phosphates. This behavior has been described in terms of resonant bonding, but puzzles remain, particularly regarding different physical properties of crystalline and amorphous phases. Here we show that there is a strong competition between ionic and covalent bonding in cubic phase providing a link between the chemical basis of phase change memory property and origins of giant responses of piezoelectric materials (PbTiO3, BiFeO3). This has important consequences for dynamical behavior in particular leading to a simultaneous hardening of acoustic modes and softening of high frequency optic modes in crystalline phase relative to amorphous. This different bonding in amorphous and crystalline phases provides a direct explanation for different physical properties and understanding of the combination of long time stability and rapid switching and may be useful in finding new phase change compositions with superior properties.

Characterization of Al-Mg Alloy Aged at Low Temperatures

DOE PAGES

Yi, Gaosong; Cullen, David A.; Littrell, Kenneth C.; ...

2017-02-06

For this research, long-term aged [343 K (70 °C) for 30 months and natural exposure for over 10 years] Al 5456 H116 samples were characterized using electron backscatter diffraction (EBSD), scanning transmission electron microscopy (STEM), state-of-the-art energy-dispersive X-ray spectroscopy (EDS) systems, and small-angle neutron scattering (SANS). ASTM G-67 mass loss tests of the sensitized Al 5456 alloy samples were conducted. Intragranular Mg-rich precipitates, such as Guinier–Preston (GP) zones, were confirmed in Al 5456 H116 aged at 343 K (70 °C) for 30 months, and the volume of these precipitates is 1.39 pct. β' phase is identified at the grain boundarymore » of a navy ship sample, while high-resolution STEM results reveal no intragranular precipitates. Intergranular corrosion (IGC) of Al 5456 was found to be related to the continuity of intergranular precipitates.« less

Heavy ion irradiations on synthetic hollandite-type materials: Ba{sub 1.0}Cs{sub 0.3}A{sub 2.3}Ti{sub 5.7}O{sub 16} (A=Cr, Fe, Al)

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

Tang, Ming, E-mail: mtang@lanl.gov; Tumurugoti, Priyatham; Clark, Braeden

2016-07-15

The hollandite supergroup of minerals has received considerable attention as a nuclear waste form for immobilization of Cs. The radiation stability of synthetic hollandite-type compounds described generally as Ba{sub 1.0}Cs{sub 0.3}A{sub 2.3}Ti{sub 5.7}O{sub 16} (A=Cr, Fe, Al) were evaluated by heavy ion (Kr) irradiations on polycrystalline single phase materials and multiphase materials incorporating the hollandite phases. Ion irradiation damage effects on these samples were examined using grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). Single phase compounds possess tetragonal structure with space group I4/m. GIXRD and TEM observations revealed that 600 keV Kr irradiation-induced amorphization on single phasemore » hollandites compounds occurred at a fluence between 2.5×10{sup 14} Kr/cm{sup 2} and 5×10{sup 14} Kr/cm{sup 2}. The critical amorphization fluence of single phase hollandite compounds obtained by in situ 1 MeV Kr ion irradiation was around 3.25×10{sup 14} Kr/cm{sup 2}. The hollandite phase exhibited similar amorphization susceptibility under Kr ion irradiation when incorporated into a multiphase system. - Graphical abstract: 600 keV Kr irradiation-induced amorphization on single phase hollandites compounds occurred at a fluence between 2.5×10{sup 14} Kr/cm{sup 2} and 5×10{sup 14} Kr/cm{sup 2}. The hollandite phase exhibited similar amorphization susceptibility under Kr ion irradiation when incorporated into a multiphase system. This is also the first time that the critical amorphization fluence of single phase hollandite compounds were determined at a fluence of around 3.25×10{sup 14} Kr/cm{sup 2} by in situ 1 MeV Kr ion irradiation. Display Omitted.« less

Effect of interphase mixing on the structure of calcium silicate intergranular film/silicon nitride crystal interfaces

NASA Astrophysics Data System (ADS)

Su, Xiaotao; Garofalini, Stephen H.

2005-06-01

Molecular-dynamics simulations of intergranular films (IGF) containing Si, O, N, and Ca in contact with Si3N4 surfaces containing different levels of interface mixing of the species from the IGF with the crystal surfaces were performed using a multibody interatomic potential. This mixing is equivalent to the formation of a roughened silicon oxynitride crystal surface. With significant interphase mixing at the crystal surfaces, less ordering into the IGF caused by the compositionally modified oxynitride interfaces is observed. Such results are in contrast to our earlier data that showed significant ordering into the IGF induced by the ideally terminated crystal surfaces with no interphase mixing. In all cases, the central position of the first peak in the Si-O pair distribution function (PDF) at the interface ranges from 1.62 to 1.64 Å, consistent with recent experimental findings. The central position of the first peak in the Si-N PDF ranges from 1.72 to 1.73 Å, consistent with experimental results. With increased interphase mixing, the intensity as well as the area of the first peak of the Si-O and Si-N PDFs for Si attached to the crystal decreases, indicating the decrease of coordination number of O or N with these silicon. Such combined decrease in coordination indicates a significant remnant of vacancies in the crystal surfaces due to the exchange process used here. The results imply a significant effect of interface roughness on the extent of ordering in the amorphous IGF induced by the crystal surface.

Local structure of the crystalline and amorphous states of Ga2Te3 phase-change alloy without resonant bonding: A combined x-ray absorption and ab initio study

NASA Astrophysics Data System (ADS)

Kolobov, A. V.; Fons, P.; Krbal, M.; Mitrofanov, K.; Tominaga, J.; Uruga, T.

2017-02-01

Phase-change memories are usually associated with GeTe-Sb2Te3 quasibinary alloys, where the large optical contrast between the crystalline and amorphous phases is attributed to the formation of resonant bonds in the crystalline phase, which has a rocksalt-like structure. The recent findings that tetrahedrally bonded Ga2Te3 possesses a similarly large property contrast and very low thermal conductivity in the crystalline phase and undergoes low-energy switching [H. Zhu et al., Appl. Phys. Lett. 97, 083504 (2010), 10.1063/1.3483762; K. Kurosaki et al., Appl. Phys. Lett. 93, 012101 (2008), 10.1063/1.2940591] challenge the existing paradigm. In this work we report on the local structure of the crystalline and amorphous phases of Ga2Te3 obtained from x-ray absorption measurements and ab initio simulations. Based on the obtained results, a model of phase change in Ga2Te3 is proposed. We argue that efficient switching in Ga2Te3 is due to the presence of primary and secondary bonding in the crystalline phase originating from the high concentration of Ga vacancies, whereas the structural stability of both phases is ensured by polyvalency of Te atoms due to the presence of lone-pair electrons and the formation of like-atom bonds in the amorphous phase.

Local bonding structure of tellurium and antimony in the phase change chalcogenides germanium-antimony-tellurium: A nuclear magnetic resonance study

NASA Astrophysics Data System (ADS)

Bobela, David C.

Recent technological applications of some chalcogenide materials, compounds containing a group VI atom, have prompted studies of the local atomic structure of the amorphous phase. In the case of Ge2Sb2Te 5, metastability in the local bonding structure is responsible for its usefulness as a phase-change memory material. There is no consensus on the exact phase-change mechanism, which is partly due to the inadequacy of standard scattering techniques to probe the structure of the amorphous phase. Nuclear magnetic resonance methods, on the other hand, are well suited to study local structural order even in the absence of a periodic lattice. In this technique, structural information is encoded as an oscillating voltage caused by the nuclear spin. For the tellurium isotope, 125Te (spin = 1/2 in the ground state), the dominant interaction comes from the core and valence electrons that carry angular momentum. This interaction is helpful in identifying Te sites of different local coordination since the number of neighboring atoms should markedly change the local electronic structure. The antimony isotope 125Sb has a spin = 5/2 in the ground state and possesses an asymmetric nuclear charge. This quadrupole moment will interact with an electric field gradient at the nuclear site, which is provided by an asymmetric electron cloud surrounding the nucleus. The frequency-space spectra will reflect the strength of the interaction as well as the symmetry of the local electronic environment. This work investigates the nuclear magnetic resonance spectrum of 125Te and 125Sb in the crystalline and amorphous forms of several GexSbyTe 1-x-y compounds where 0 < (x, y) < 1. Results from the crystalline phase 125Te data show a trend in the spectral position that can be related to the tellurium bonded to three and six neighbors. In the amorphous phase, the same trend is observed, and the nuclear magnetic resonance fingerprint of two-fold and three-fold coordinated tellurium is obtained. It is concluded, based upon this comparison that the Te atoms see a dramatically different bonding environment depending on which phase the lattice has. The 125Sb data for the crystalline phase indicate electric field gradients that are consistent with similarly bonded quadrupolar nuclei, such as Sb atoms in crystalline Sb or five-fold coordinated Sb in crystalline MnSb. The NMR data exemplify the consequences of combinatorial disorder on the spectra via the absence of certain line-shape features. In the amorphous phase, the electric field gradients are approximately seven times larger, and the fingerprints of both highly-symmetric and asymmetric antimony sites emerge. Details of field gradient, i.e. the magnitude and symmetry, are remarkably similar to those found in Sb containing compounds where the Sb sites are three-fold pyramidal, such as in crystalline Sb2X3 where X = O, S, or Se. The observations from the NMR data provide a critical litmus test for recent structural models of the amorphous phase. In particular, the amorphous phase data provides clear evidence that the Te atoms are two-fold and three-fold coordinated while the Sb atoms are most likely bonded in three-fold pyramidal configurations. These observations imply a structural model of the amorphous phase that agrees best with a models based upon the "8 minus n", or "8-n" rule for chemical bonding in amorphous semiconductors. Thus, the lattice of these compounds is arranged such that the constituent elements have enough bonds, on average, to satisfy their valence requirement. The implications of the NMR data on theoretical modeling data are immediate. Theoretical models of these systems must possess some aspect of the "8-n" mentality. With this idea as a foundation for physically realistic representations of the amorphous phase, the origin of the phase-change mechanism may be unraveled, which will ultimately speed the process of compositional optimization of phase-change materials.

Processing Bi-Pb-Sr-Ca-Cu-O superconductors from amorphous state

NASA Technical Reports Server (NTRS)

Chiang, C. K.; Wong-Ng, W.; Cook, L. P.; Freiman, S. W.; Hwang, N. M.; Vaudin, M.; Hill, M. D.; Shull, R. D.; Shapiro, A. J.; Swartzendruber, L. J.

1991-01-01

The bismuth based high T sub c superconductors can be processed via an amorphous Bi-Pb-Sr-Ca-Cu oxide. The amorphous oxides were prepared by melting the constituent powders in an alumina crucible at 1200 C in air followed by pouring the liquid onto an aluminum plate, and rapidly pressing with a second plate. In the amorphous state, no crystalline phase was identified in the powder x ray diffraction pattern of the quenched materials. After heat treatment at high temperature the amorphous materials crystallized into a glass ceramic containing a large fraction of the Bi2Sr2Ca2Cu3O(x) phase T sub c = 110 K. The processing method, crystallization, and results of dc electrical resistivity and ac magnetic susceptibility measurements are discussed.

Influence of the exchange and correlation functional on the structure of amorphous InSb and In{sub 3}SbTe{sub 2} compounds

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

Gabardi, Silvia; Caravati, Sebastiano; Bernasconi, Marco, E-mail: marco.bernasconi@mater.unimib.it

2016-05-28

We have investigated the structural, vibrational, and electronic properties of the amorphous phase of InSb and In{sub 3}SbTe{sub 2} compounds of interest for applications in phase change non-volatile memories. Models of the amorphous phase have been generated by quenching from the melt by molecular dynamics simulations based on density functional theory. In particular, we have studied the dependence of the structural properties on the choice of the exchange-correlation functional. It turns out that the use of the Becke-Lee-Yang-Parr functional provides models with a much larger fraction of In atoms in a tetrahedral bonding geometry with respect to previous results obtainedmore » with the most commonly used Perdew-Becke-Ernzerhof functional. This outcome is at odd with the properties of Ge{sub 2}Sb{sub 2}Te{sub 5} phase change compound for which the two exchange-correlation functionals yield very similar results on the structure of the amorphous phase.« less

Hot tensile tests of Inconel 718

NASA Technical Reports Server (NTRS)

1980-01-01

The physical metallurgy of near-solidus integranular cracking in Inconel 718 welds was investigated. The data, although inconclusive, suggest at least two mechanisms which might explain intergranular cracking (microfissuring) in the heat-affected zone of several high temperature alloys. One theory is based on the separation of intergranular liquid while the other involves mechanical failure of solid ligaments surrounded by intergranular liquid. Both mechanisms concentrate strain in the grain boundaries resulting in low strain (1%) intergranular brittleness. The mechanisms reported might also pertain to the physical metallurgy of casting, powder metallurgy sintering and hot isostatic pressing.

Spontaneous crystalline-to-amorphous phase transformation of organic or medicinal compounds in the presence of porous media, part 2: amorphization capacity and mechanisms of interaction.

PubMed

Qian, Ken K; Suib, Steven L; Bogner, Robin H

2011-11-01

Amorphization of crystalline compounds using mesoporous media is a promising technique to improve the solubility and dissolution rate of poorly soluble compounds. The objective of this paper is to determine the capacity of amorphization and understand the mechanisms of phase transformation. Commercial grades of mesoporous silicon dioxide (SiO(2)) samples (5- to 30-nm mean pore diameters) with either constant surface area or constant pore volume were used. The amorphization capacity of naphthalene was not proportional to either the surface area or the pore volume measured using adsorption chambers. Instead, the amorphization capacity correlated with surface curvature, that is, the smaller the pore diameter and the higher the surface curvature, the greater the amorphization capacity. The change in surface chemistry due to a highly curved surface may be responsible for the enhanced amorphization capacity as well. The amorphization of crystalline compounds was facilitated through capillary condensation, with the decrease in pore volume as the direct experimental evidence. The amorphization capacity was also enhanced by the dipole-dipole or dipole-induced dipole interaction, promoted by the hydroxyl groups on the surface of SiO(2). The enthalpy of vapor-solid condensation of crystalline compounds was a useful indicator to predict the rank order of amorphization capacity. Copyright © 2011 Wiley-Liss, Inc.

Activation of weak IR fundamentals of two species of astrochemical interest in the T(d) point group--the importance of amorphous ices.

PubMed

Hudson, R L; Gerakines, P A; Loeffler, M J

2015-05-21

New measurements are reported on the weak ν1 and ν2 fundamentals of frozen CH4, a solid of considerable astrochemical interest. Infrared spectra in the ν1 and ν2 regions are presented for three CH4-ice phases at 10-30 K with new absorption coefficients and band strengths to quantify the results. In contrast to the situation with the two crystalline phases of CH4, both ν1 and ν2 were seen clearly in methane's amorphous phase. To support our CH4 work, we also present new results for NH4SH, a component of Jupiter's atmosphere, showing that the ν2 vibration of NH4(+) undergoes a dramatic loss of intensity during an amorphous-to-crystalline phase transition, but is regenerated in equally-dramatic fashion by radiation-induced amorphization of the sample. Results are compared to work recently published in this journal and elsewhere.

Dilution effect on the formation of amorphous phase in the laser cladded Ni-Fe-B-Si-Nb coatings after laser remelting process

NASA Astrophysics Data System (ADS)

Li, Ruifeng; Li, Zhuguo; Huang, Jian; Zhu, Yanyan

2012-08-01

Ni-Fe-B-Si-Nb coatings have been deposited on mild steel substrates using high power diode laser cladding. Scanning laser beam at high speeds was followed to remelt the surface of the coatings. Different laser cladding powers in the range of 700-1000 W were used to obtain various dilution ratios in the coating. The dilution effect on the chemical characterization, phase composition and microstructure is analyzed by energy dispersive spectroscopy, X-ray diffraction and scanning-electron microscopy. The microhardness distribution of the coatings after laser processing is also measured. The results reveal that Ni-based amorphous composite coatings have successfully been fabricated on mild steel substrate at low dilution ratio when the cladding power was 700 W, 800 W and 900 W. While at high laser power of 1000 W, no amorphous phase was found. The coatings with low dilution ratio exhibit the highest microhardness of 1200 HV0.5 due to their largest volume fraction of amorphous phase.

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

Characterizing the Phyllosilicates and Amorphous Phases Found by MSL Using Laboratory XRD and EGA Measurements of Natural and Synthetic Materials

NASA Technical Reports Server (NTRS)

Rampe, Elizabeth B.; Morris, Richard V.; Chipera, Steve; Bish, David L.; Bristow, Thomas; Archer, Paul Douglas; Blake, David; Achilles, Cherie; Ming, Douglas W.; Vaniman, David;

Far-infrared spectral studies of phase changes in water ice induced by proton irradiation

NASA Technical Reports Server (NTRS)

Moore, Marla H.; Hudson, Reggie L.

1992-01-01

Changes in the FIR spectrum of crystalline and amorphous water ice as a function of temperature are reported. The dramatic differences between the spectra of these ices in the FIR are used to examine the effect of proton irradiation on the stability of the crystalline and amorphous ice phases from 13 to 77 K. In particular, the spectra near 13 K show interconversion between the amorphous and crystalline ice phases beginning at doses near 2 eV/molecule and continuing cyclically with increased dose. The results are used to estimate the stability of irradiated ices in astronomical environments.

A Novel High-Density Phase and Amorphization of Nitrogen-Rich 1H-Tetrazole (CH2N4) under High Pressure

PubMed Central

Li, Wenbo; Huang, Xiaoli; Bao, Kuo; Zhao, Zhonglong; Huang, Yanping; Wang, Lu; Wu, Gang; Zhou, Bo; Duan, Defang; Li, Fangfei; Zhou, Qiang; Liu, Bingbing; Cui, Tian

2017-01-01

The high-pressure behaviors of nitrogen-rich 1H-tetrazole (CH2N4) have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman scattering up to 75 GPa. A first crystalline-to-crystalline phase transition is observed and identified above ~3 GPa with a large volume collapse (∼18% at 4.4 GPa) from phase I to phase II. The new phase II forms a dimer-like structure, belonging to P1 space group. Then, a crystalline-to-amorphous phase transition takes place over a large pressure range of 13.8 to 50 GPa, which is accompanied by an interphase region approaching paracrystalline state. When decompression from 75 GPa to ambient conditions, the final product keeps an irreversible amorphous state. Our ultraviolet (UV) absorption spectrum suggests the final product exhibits an increase in molecular conjugation. PMID:28218236

Phase formation polycrystalline vanadium oxide via thermal annealing process under controlled nitrogen pressure

NASA Astrophysics Data System (ADS)

Jessadaluk, S.; Khemasiri, N.; Rahong, S.; Rangkasikorn, A.; Kayunkid, N.; Wirunchit, S.; Horprathum, M.; Chananonnawathron, C.; Klamchuen, A.; Nukeaw, J.

2017-09-01

This article provides an approach to improve and control crystal phases of the sputtering vanadium oxide (VxOy) thin films by post-thermal annealing process. Usually, as-deposited VxOy thin films at room temperature are amorphous phase: post-thermal annealing processes (400 °C, 2 hrs) under the various nitrogen (N2) pressures are applied to improve and control the crystal phase of VxOy thin films. The crystallinity of VxOy thin films changes from amorphous to α-V2O5 phase or V9O17 polycrystalline, which depend on the pressure of N2 carrier during annealing process. Moreover, the electrical resistivity of the VxOy thin films decrease from 105 Ω cm (amorphous) to 6×10-1 Ω cm (V9O17). Base on the results, our study show a simply method to improve and control phase formation of VxOy thin films.

A Novel High-Density Phase and Amorphization of Nitrogen-Rich 1H-Tetrazole (CH2N4) under High Pressure.

PubMed

Li, Wenbo; Huang, Xiaoli; Bao, Kuo; Zhao, Zhonglong; Huang, Yanping; Wang, Lu; Wu, Gang; Zhou, Bo; Duan, Defang; Li, Fangfei; Zhou, Qiang; Liu, Bingbing; Cui, Tian

2017-02-20

The high-pressure behaviors of nitrogen-rich 1H-tetrazole (CH 2 N 4 ) have been investigated by in situ synchrotron X-ray diffraction (XRD) and Raman scattering up to 75 GPa. A first crystalline-to-crystalline phase transition is observed and identified above ~3 GPa with a large volume collapse (∼18% at 4.4 GPa) from phase I to phase II. The new phase II forms a dimer-like structure, belonging to P1 space group. Then, a crystalline-to-amorphous phase transition takes place over a large pressure range of 13.8 to 50 GPa, which is accompanied by an interphase region approaching paracrystalline state. When decompression from 75 GPa to ambient conditions, the final product keeps an irreversible amorphous state. Our ultraviolet (UV) absorption spectrum suggests the final product exhibits an increase in molecular conjugation.

A thermodynamic approach to model the caloric properties of semicrystalline polymers

NASA Astrophysics Data System (ADS)

Lion, Alexander; Johlitz, Michael

2016-05-01

It is well known that the crystallisation and melting behaviour of semicrystalline polymers depends in a pronounced manner on the temperature history. If the polymer is in the liquid state above the melting point, and the temperature is reduced to a level below the glass transition, the final degree of crystallinity, the amount of the rigid amorphous phase and the configurational state of the mobile amorphous phase strongly depend on the cooling rate. If the temperature is increased afterwards, the extents of cold crystallisation and melting are functions of the heating rate. Since crystalline and amorphous phases exhibit different densities, the specific volume depends also on the temperature history. In this article, a thermodynamically based phenomenological approach is developed which allows for the constitutive representation of these phenomena in the time domain. The degree of crystallinity and the configuration of the amorphous phase are represented by two internal state variables whose evolution equations are formulated under consideration of the second law of thermodynamics. The model for the specific Gibbs free energy takes the chemical potentials of the different phases and the mixture entropy into account. For simplification, it is assumed that the amount of the rigid amorphous phase is proportional to the degree of crystallinity. An essential outcome of the model is an equation in closed form for the equilibrium degree of crystallinity in dependence on pressure and temperature. Numerical simulations demonstrate that the process dependences of crystallisation and melting under consideration of the glass transition are represented.

High performance of SDC and GDC core shell type composite electrolytes using methane as a fuel for low temperature SOFC

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

Irshad, Muneeb; Siraj, Khurram, E-mail: razahussaini786@gmail.com, E-mail: khurram.uet@gmail.com; Javed, Fayyaz

Nanocomposites Samarium doped Ceria (SDC), Gadolinium doped Ceria (GDC), core shell SDC amorphous Na{sub 2}CO{sub 3} (SDCC) and GDC amorphous Na{sub 2}CO{sub 3} (GDCC) were synthesized using co-precipitation method and then compared to obtain better solid oxide electrolytes materials for low temperature Solid Oxide Fuel Cell (SOFCs). The comparison is done in terms of structure, crystallanity, thermal stability, conductivity and cell performance. In present work, XRD analysis confirmed proper doping of Sm and Gd in both single phase (SDC, GDC) and dual phase core shell (SDCC, GDCC) electrolyte materials. EDX analysis validated the presence of Sm and Gd in bothmore » single and dual phase electrolyte materials; also confirming the presence of amorphous Na{sub 2}CO{sub 3} in SDCC and GDCC. From TGA analysis a steep weight loss is observed in case of SDCC and GDCC when temperature rises above 725 °C while SDC and GDC do not show any loss. The ionic conductivity and cell performance of single phase SDC and GDC nanocomposite were compared with core shell GDC/amorphous Na{sub 2}CO{sub 3} and SDC/ amorphous Na{sub 2}CO{sub 3} nanocomposites using methane fuel. It is observed that dual phase core shell electrolytes materials (SDCC, GDCC) show better performance in low temperature range than their corresponding single phase electrolyte materials (SDC, GDC) with methane fuel.« less

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

DOE PAGES

Mu, Linqin; Lin, Ruoqian; Xu, Rong; ...

2018-04-18

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

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

Mu, Linqin; Lin, Ruoqian; Xu, Rong

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Observation of polyamorphism in the phase change alloy Ge1Sb2Te4

NASA Astrophysics Data System (ADS)

Kalkan, B.; Sen, S.; Cho, J.-Y.; Joo, Y.-C.; Clark, S. M.

2012-10-01

A high-pressure synchrotron x-ray diffraction study of the phase change alloy Ge1Sb2Te4 demonstrates the existence of a polyamorphic phase transition between the "as deposited" low density amorphous (LDA) phase and a high density amorphous (HDA) phase at ˜10 GPa. The entropy of the HDA phase is expected to be higher than that of the LDA phase resulting in a negative Clapeyron slope for this transition. These phase relations may enable the polyamorphic transition to play a role in the memory and data storage applications.

Density functional simulations of Sb-rich GeSbTe phase change alloys.

PubMed

Gabardi, S; Caravati, S; Bernasconi, M; Parrinello, M

2012-09-26

We generated models of the amorphous phase of Sb-rich GeSbTe phase change alloys by quenching from the melt within density functional molecular dynamics. We considered the two compositions Ge(1)Sb(1)Te(1) and Ge(2)Sb(4)Te(5). Comparison with previous results on the most studied Ge(2)Sb(2)Te(5) allowed us to draw some conclusions on the dependence of the structural properties of the amorphous phase on the alloy composition. Vibrational and electronic properties were also scrutinized. Phonons at high frequencies above 200 cm(-1) are localized in tetrahedra around Ge atoms in Sb-rich compounds as well as in Ge(2)Sb(2)Te(5). All compounds are semiconducting in the amorphous phase, with a band gap in the range 0.7-1.0 eV.

Density functional simulations of Sb-rich GeSbTe phase change alloys

NASA Astrophysics Data System (ADS)

Gabardi, S.; Caravati, S.; Bernasconi, M.; Parrinello, M.

2012-09-01

We generated models of the amorphous phase of Sb-rich GeSbTe phase change alloys by quenching from the melt within density functional molecular dynamics. We considered the two compositions Ge1Sb1Te1 and Ge2Sb4Te5. Comparison with previous results on the most studied Ge2Sb2Te5 allowed us to draw some conclusions on the dependence of the structural properties of the amorphous phase on the alloy composition. Vibrational and electronic properties were also scrutinized. Phonons at high frequencies above 200 cm-1 are localized in tetrahedra around Ge atoms in Sb-rich compounds as well as in Ge2Sb2Te5. All compounds are semiconducting in the amorphous phase, with a band gap in the range 0.7-1.0 eV.

Size-dependent pressure-induced amorphization: a thermodynamic panorama.

PubMed

Machon, Denis; Mélinon, Patrice

2015-01-14

Below a critical particle size, some pressurized compounds (e.g. TiO2, Y2O3, PbTe) undergo a crystal-to-amorphous transformation instead of a polymorphic transition. This effect reflects the greater propensity of nanomaterials for amorphization. In this work, a panorama of thermodynamic interpretations is given: first, a descriptive analysis based on the energy landscape concept gives a general comprehension of the balance between thermodynamics and kinetics to obtain an amorphous state. Then, a formal approach based on Gibbs energy to describe the thermodynamics and phase transitions in nanoparticles gives a basic explanation of size-dependent pressure-induced amorphization. The features of this transformation (amorphization occurs at pressures lower than the polymorphic transition pressure!) and the nanostructuration can be explained in an elaborated model based on the Ginzburg-Landau theory of phase transition and on percolation theory. It is shown that the crossover between polymorphic transition and amorphization is highly dependent on the defect density and interfacial energy, i.e., on the synthesis process. Their behavior at high pressure is a quality control test for the nanoparticles.

Tungsten solution kinetics and amorphization of nickel in mechanically alloyed Ni-W alloys

NASA Technical Reports Server (NTRS)

Aning, A. O.; Wang, Z.; Courtney, T. H.

1993-01-01

The kinetics of solution of W, and the subsequent amorphization of Ni, in mechanically alloyed Ni-W alloys has been investigated. As W is a highly abrasive material in the energy intensive devices used for mechanical alloying, we studied the above reactions in different mills. One used hardened steel balls as the grinding media, and the other Al2O3. Abrasion is common to both mills, but Fe wear debris from the hardened steel enters into solution in the Ni rich phases whereas Al2O3 debris is present as small dispersoids. The kinetics of W solution and those of subsequent amorphization do not appear strongly affected by the Fe in solution or the Al2O3 dispersoid. Tungsten dissolves in crystalline Ni in amounts in excess of the equilibrium solubility during alloying. Amorphization of the Ni phase occurs if the W content in this phase exceeds ca. 28 at. pct.

Pressure-Induced Amorphization and a New High Density Amorphous Metallic Phase in Matrix-Free Ge Nanoparticles.

PubMed

Corsini, Niccolo R C; Zhang, Yuanpeng; Little, William R; Karatutlu, Ali; Ersoy, Osman; Haynes, Peter D; Molteni, Carla; Hine, Nicholas D M; Hernandez, Ignacio; Gonzalez, Jesus; Rodriguez, Fernando; Brazhkin, Vadim V; Sapelkin, Andrei

2015-11-11

Over the last two decades, it has been demonstrated that size effects have significant consequences for the atomic arrangements and phase behavior of matter under extreme pressure. Furthermore, it has been shown that an understanding of how size affects critical pressure-temperature conditions provides vital guidance in the search for materials with novel properties. Here, we report on the remarkable behavior of small (under ~5 nm) matrix-free Ge nanoparticles under hydrostatic compression that is drastically different from both larger nanoparticles and bulk Ge. We discover that the application of pressure drives surface-induced amorphization leading to Ge-Ge bond overcompression and eventually to a polyamorphic semiconductor-to-metal transformation. A combination of spectroscopic techniques together with ab initio simulations were employed to reveal the details of the transformation mechanism into a new high density phase-amorphous metallic Ge.

500 keV Ar2+ ion irradiation induced anatase to brookite phase transformation and ferromagnetism at room temperature in TiO2 thin films

NASA Astrophysics Data System (ADS)

Bharati, B.; Mishra, N. C.; Kanjilal, D.; Rath, Chandana

2018-01-01

In our earlier report, where we have demonstrated ferromagnetic behavior at room temperature (RT) in TiO2 thin films deposited through electron beam evaporation technique followed by annealing either in Ar or O2 atmosphere [Mohanty et al., Journal of Magnetism and Magnetic Materials 355 (2014) 240-245], here we have studied the evolution of structure and magnetic properties after irradiating the TiO2 thin films with 500 keV Ar2+ ions. The pristine film while exhibits anatase phase, the films become amorphous after irradiating at fluence in the range 1 × 1014 to 1 × 1016 ions/cm2. Increasing the fluence up to 5 × 1016 ions/cm2, amorphous to crystalline phase transformation occurs and the structure becomes brookite. Although anatase to rutile phase transformation is usually reported in literatures, anatase to brookite phase transformation is an unusual feature which we have reported here for the first time. Such anatase to brookite phase transformation is accompanied with grain growth without showing any change in film thickness evidenced from Rutherford's Back Scattering (RBS) measurement. From scanning probe micrographs (SPM), roughness is found to be more in amorphous films than in the crystalline ones. Anatase to brookite phase transformation could be realized by considering the importance of intermediate amorphous phase. Because due to amorphous phase, heat deposited by energetic ions are localized as dissipation of heat is less and as a result, the localized region crystallizes in brookite phase followed by grain growth as observed in highest fluence. Further, we have demonstrated ferromagnetic behavior at RT in irradiated films similar to pristine one, irrespective of their phase and crystallinity. Origin for room temperature ferromagnetism (RTFM) is attributed to the presence of oxygen vacancies which is confirmed by carrying out XPS measurement.

Redshifted and blueshifted photoluminescence emission of InAs/InP quantum dots upon amorphization of phase change material.

PubMed

Humam, Nurrul Syafawati Binti; Sato, Yu; Takahashi, Motoki; Kanazawa, Shohei; Tsumori, Nobuhiro; Regreny, Philippe; Gendry, Michel; Saiki, Toshiharu

2014-06-16

We present the mechanisms underlying the redshifted and blueshifted photoluminescence (PL) of quantum dots (QDs) upon amorphization of phase change material (PCM). We calculated the stress and energy shift distribution induced by volume expansion using finite element method. Simulation result reveals that redshift is obtained beneath the flat part of amorphous mark, while blueshift is obtained beneath the edge region of amorphous mark. Simulation result is accompanied by two experimental studies; two-dimensional PL intensity mapping of InAs/InP QD sample deposited by a layer of PCM, and an analysis on the relationship between PL intensity ratio and energy shift were performed.

Interface amorphization in hexagonal boron nitride films on sapphire substrate grown by metalorganic vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Yang, Xu; Nitta, Shugo; Pristovsek, Markus; Liu, Yuhuai; Nagamatsu, Kentaro; Kushimoto, Maki; Honda, Yoshio; Amano, Hiroshi

2018-05-01

Hexagonal boron nitride (h-BN) films directly grown on c-plane sapphire substrates by pulsed-mode metalorganic vapor phase epitaxy exhibit an interlayer for growth temperatures above 1200 °C. Cross-sectional transmission electron microscopy shows that this interlayer is amorphous, while the crystalline h-BN layer above has a distinct orientational relationship with the sapphire substrate. Electron energy loss spectroscopy shows the energy-loss peaks of B and N in both the amorphous interlayer and the overlying crystalline h-BN layer, while Al and O signals are also seen in the amorphous interlayer. Thus, the interlayer forms during h-BN growth through the decomposition of the sapphire at elevated temperatures.

High pressure synthesis of amorphous TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Li, Quanjun; Liu, Ran; Wang, Tianyi; Xu, Ke; Dong, Qing; Liu, Bo; Liu, Jing; Liu, Bingbing

2015-09-01

Amorphous TiO2 nanotubes with diameters of 8-10 nm and length of several nanometers were synthesized by high pressure treatment of anatase TiO2 nanotubes. The structural phase transitions of anatase TiO2 nanotubes were investigated by using in-situ high-pressure synchrotron X-ray diffraction (XRD) method. The starting anatase structure is stable up to ˜20GPa, and transforms into a high-density amorphous (HDA) form at higher pressure. Pressure-modified high- to low-density transition was observed in the amorphous form upon decompression. The pressure-induced amorphization and polyamorphism are in good agreement with the previous results in ultrafine TiO2 nanoparticles and nanoribbons. The relationship between the LDA form and α-PbO2 phase was revealed by high-resolution transmission electron microscopy (HRTEM) study. In addition, the bulk modulus (B0 = 158 GPa) of the anatase TiO2 nanotubes is smaller than those of the corresponding bulks and nanoparticles (180-240 GPa). We suggest that the unique open-ended nanotube morphology and nanosize play important roles in the high pressure phase transition of TiO2 nanotubes.

Development of High Strength Ni-Cu-Zr-Ti-Si-Sn In-Situ Bulk Metallic Glass Composites Reinforced by Hard B2 Phase

NASA Astrophysics Data System (ADS)

Park, Hyo Jin; Hong, Sung Hwan; Park, Hae Jin; Kim, Young Seok; Kim, Jeong Tae; Na, Young Sang; Lim, Ka Ram; Wang, Wei-Min; Kim, Ki Buem

2018-03-01

In the present study, the influence of atomic ratio of Zr to Ti on the microstructure and mechanical properties of Ni-Cu-Zr-Ti-Si-Sn alloys is investigated. The alloys were designed by fine replacement of Ti for Zr from Ni39Cu20Zr36-xTixSi2Sn3. The increase of Ti content enhances glass forming ability of the alloy by suppression of formation of (Ni, Cu)10(Zr, Ti)7 phase during solidification. With further increasing Ti content up to 24 at.%, the B2 phase is introduced in the amorphous matrix with a small amount of B19' phase from alloy melt. The bulk metallic glass composite containing B2 phase with a volume fraction of 10 vol% exhibits higher fracture strength ( 2.5 GPa) than that of monolithic bulk metallic glass ( 2.3 GPa). This improvement is associated to the individual mechanical characteristics of the B2 phase and amorphous matrix. The B2 phase exhibits higher hardness and modulus than those of amorphous matrix as well as effective stress accommodation up to the higher stress level than the yield strength of amorphous matrix. The large stress accommodation capacity of the hard B2 phase plays an important factor to improve the mechanical properties of in situ Ni-based bulk metallic glass composites.

Formation and structure of Al-Zr metallic glasses studied by Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Li, J. H.; Zhao, S. Z.; Dai, Y.; Cui, Y. Y.; Liu, B. X.

2011-06-01

Based on the recently constructed n-body potential, both molecular dynamics and Monte Carlo simulations revealed that the Al-Zr amorphous alloy or metallic glass can be obtained within the composition range of 24-66 at. % Zr. The revealed composition range could be considered the intrinsic glass-forming range and it quantitatively indicates the glass-forming ability of the Al-Zr system. The underlying physics of the finding is that, within the composition range, the amorphous alloys are energetically favored to form. In addition, it is proposed that the energy difference between a solid solution and the amorphous phase could serve as the driving force of the crystalline to amorphous transition and the driving force should be sufficiently large for amorphization to take place. The minimum driving forces for fcc Al-based and hcp Zr-based Al-Zr solid solutions to amorphize are calculated to be about -0.05 and -0.03 eV/atom, respectively, whereas the maximum driving force is found to be -0.23 eV/atom at the alloy stoichiometry of Al60Zr40. A thermodynamics parameter γ¯, defined as the ratio of the driving force to the formation energy of the solid solution, is further proposed to indicate the glass-forming ability of an Al-Zr alloy. Thermodynamics calculations show that the glass-forming ability of the Al56Zr44 alloy is the largest, implying that the Al56Zr44 amorphous alloy is more ready to form than other alloys in the Al-Zr system. Besides, Voronoi analysis found that there exists a strong correlation between the coordinate number and structure. Amorphization could result in increase of coordinate numbers and about 1.5% volume-expansion. The volume-expansion induced by amorphization can be attributed to two factors, i.e., the total bond number of the Al-Zr amorphous phase is greater than that of the corresponding solid solution, and the averaged bond length of the Al-Zr amorphous phase is longer than that of the corresponding solid solution. For the Al-Zr alloys, especially for the Al-Zr amorphous phase, there exists a negative chemical micro-inhomogeneity in the alloys, suggesting that metallic bonds prefer to be formed between the atoms of dissimilar species. Finally, it is found that there is a weak correspondence between the bond-angle distributions of Al-Zr amorphous alloys and the solid solutions. It is further suggested that the configuration of Al-Zr amorphous alloys embodies some hybrid imprint of bcc, fcc, and hcp structures. More interestingly, the short-range order is also observed in the bond-angle distributions.

Method to quantify the delocalization of electronic states in amorphous semiconductors and its application to assessing charge carrier mobility of p -type amorphous oxide semiconductors

NASA Astrophysics Data System (ADS)

de Jamblinne de Meux, A.; Pourtois, G.; Genoe, J.; Heremans, P.

2018-01-01

Amorphous semiconductors are usually characterized by a low charge carrier mobility, essentially related to their lack of long-range order. The development of such material with higher charge carrier mobility is hence challenging. Part of the issue comes from the difficulty encountered by first-principles simulations to evaluate concepts such as the electron effective mass for disordered systems since the absence of periodicity induced by the disorder precludes the use of common concepts derived from condensed matter physics. In this paper, we propose a methodology based on first-principles simulations that partially solves this problem, by quantifying the degree of delocalization of a wave function and of the connectivity between the atomic sites within this electronic state. We validate the robustness of the proposed formalism on crystalline and molecular systems and extend the insights gained to disordered/amorphous InGaZnO4 and Si. We also explore the properties of p -type oxide semiconductor candidates recently reported to have a low effective mass in their crystalline phases [G. Hautier et al., Nat. Commun. 4, 2292 (2013), 10.1038/ncomms3292]. Although in their amorphous phase none of the candidates present a valence band with delocalization properties matching those found in the conduction band of amorphous InGaZnO4, three of the seven analyzed materials show some potential. The most promising candidate, K2Sn2O3 , is expected to possess in its amorphous phase a slightly higher hole mobility than the electron mobility in amorphous silicon.

Amorphization and reduction of thermal conductivity in porous silicon by irradiation with swift heavy ions

NASA Astrophysics Data System (ADS)

Newby, Pascal J.; Canut, Bruno; Bluet, Jean-Marie; Gomès, Séverine; Isaiev, Mykola; Burbelo, Roman; Termentzidis, Konstantinos; Chantrenne, Patrice; Fréchette, Luc G.; Lysenko, Vladimir

2013-07-01

In this article, we demonstrate that the thermal conductivity of nanostructured porous silicon is reduced by amorphization and also that this amorphous phase in porous silicon can be created by swift (high-energy) heavy ion irradiation. Porous silicon samples with 41%-75% porosity are irradiated with 110 MeV uranium ions at six different fluences. Structural characterisation by micro-Raman spectroscopy and SEM imaging show that swift heavy ion irradiation causes the creation of an amorphous phase in porous Si but without suppressing its porous structure. We demonstrate that the amorphization of porous silicon is caused by electronic-regime interactions, which is the first time such an effect is obtained in crystalline silicon with single-ion species. Furthermore, the impact on the thermal conductivity of porous silicon is studied by micro-Raman spectroscopy and scanning thermal microscopy. The creation of an amorphous phase in porous silicon leads to a reduction of its thermal conductivity, up to a factor of 3 compared to the non-irradiated sample. Therefore, this technique could be used to enhance the thermal insulation properties of porous Si. Finally, we show that this treatment can be combined with pre-oxidation at 300 °C, which is known to lower the thermal conductivity of porous Si, in order to obtain an even greater reduction.

Bringing nanomagnetism to the mesoscale with artificial amorphous structures

NASA Astrophysics Data System (ADS)

Muscas, G.; Brucas, R.; Jönsson, P. E.

2018-05-01

In the quest for materials with emergent or improved properties, an effective route is to create artificial superstructures. Novel properties emerge from the coupling between the phases, but the strength of this coupling depends on the quality of the interfaces. Atomic control of crystalline interfaces is notoriously complicated and to elude that obstacle, we suggest here an all-amorphous design. Starting from a model amorphous iron alloy, we locally tune the magnetic behavior by creating boron-doped regions by means of ion implantation through a lithographic mask. This process preserves the amorphous environment, creating a non-topographic magnetic superstructure with smooth interfaces and no structural discontinuities. The absence of inhomogeneities acting as pinning centers for the magnetization reversal is demonstrated by the formation of magnetic vortexes for ferromagnetic disks as large as 20 µm in diameter embedded within a paramagnetic matrix. Rigid exchange coupling between two amorphous ferromagnetic phases in a microstructured sample is evidenced by an investigation involving first-order reversal curves. The sample consists of a soft matrix with embedded elements constituting a hard phase where the anisotropy originates from an elongated shape of the elements. We provide an intuitive explanation for the micrometer-range exchange coupling mechanism and discuss how to tailor the properties of all-amorphous superstructures.

Diffusion of lithium ions in amorphous and crystalline PEO3:LiCF3SO3 polymer electrolytes: ab initio calculations and simulations

NASA Astrophysics Data System (ADS)

Xue, Sha; Liu, Yingdi; Li, Yaping; Teeters, Dale; Crunkleton, Daniel; Wang, Sanwu

The PEO3:LiCF3SO3 polymer electrolyte has attracted significant research due to its high conductivity and enhanced stability in lithium polymer batteries. Most experimental studies have shown that amorphous PEO lithium salt electrolytes have higher conductivity than the crystalline ones. Other studies, however, have shown that crystalline phase can conduct ions. In this work, we use ab initio molecular dynamics simulations to obtain the amorphous structure of PEO3:LiCF3SO3. The diffusion pathways and activation energies of lithium ions in both crystalline and amorphous PEO3:LiCF3SO3 are determined with first-principles density functional theory. In crystalline PEO3:LiCF3SO3, the activation energy for the low-barrier diffusion pathway is approximately 1.0 eV. In the amorphous phase, the value is 0.6 eV. This result would support the experimental observation that amorphous PEO3:LiCF3SO3has higher ionic conductivity than the crystalline phase. This work was supported by NASA Grant No. NNX13AN01A and by Tulsa Institute of Alternative Energy and Tulsa Institute of Nanotechnology. This research used resources of XSEDE, NERSC, and the Tandy Supercomputing Center.

The Effects of Applied Stress and Sensitization on the Passive Film Stability of Al-Mg Alloys

DTIC Science & Technology

2013-06-01

and residual tensile and compressive stresses impact the passive layer film and the material’s electrochemistry. Sample plates of AA5083 were...electrochemistry. Sample plates of AA5083 were sensitized to different levels to promote the formation of intergranular β phase (Al3Mg2). The...41  A.  MATERIAL PROCESSING: FABRICATION AND APPLIED STRESSES OF TEST SAMPLES

Microstructural-Scale Model for Surfaces Spreading of Intergranular Corrosion in Sensitized Stainless Steels and Aluminum-Magnesium (AA5XXX) Alloys

NASA Astrophysics Data System (ADS)

Jain, Swati

Components from AA5XXX (Al-Mg alloys with more than 3 wt% Mg) alloys are X attractive due to availability of low cost, high strength to weight ratio and good weldability. Therefore, these alloys have potential applications in Naval ships. However, these alloys become susceptible to IGC (intergranular corrosion) due to beta-phase precipitation due to improper heat treatment or inadvertent thermal exposure. Stainless steels may also become susceptible due to carbide precipitation and chromium depletion on grain boundaries. IGC susceptibility depends on the interplay between the metallurgical conditions, electrochemical conditions, and chemical conditions. Specific combinations cause IGC while others do not. The objective of this study is to investigate the conditions which bring about surface spreading of IGC in these alloy classes. To accomplish this goal, a microstructure scale model was developed with experimental inputs to understand the 2-D IGC spreading in stainless steels and AA5XXX alloys. The conditions strongly affecting IGC spreading were elucidated. Upon natural and artificial aging, the stainless steels become susceptible to intergranular corrosion because of chromium depletion in the grain boundaries. After aging Al-Mg (AA5XXX) alloys show susceptibility due to the precipitation of the beta-phase (Al3Mg7) in the grain boundaries. Chromium depleted grain boundaries in stainless steels are anodically more active as compared to the interior of the grains. (3-phase rich grain boundaries have lower OCP (open circuit potential) and pitting potentials as compared to the Al-Mg solid solutions. A new approach to modeling the IGC surface spreading in polycrystalline materials that is presented. This model is the first to couple several factors into one granular scale model that illustrates the way in which they interact and IGC occurs. It sheds new information on conditions which cause IGC spreading in two alloy classes and describes a new theory for the critical potential associated with IGC. The outcomes from this contribute to ways to advance the goal of corrosion resistant computational design of alloys, guiding mitigation strategies for suppressing IGC in existing alloys, and to damage prognosis aimed at predicting damage and structural integrity.

Intergranular stress study of TC11 titanium alloy after laser shock peening by synchrotron-based high-energy X-ray diffraction

NASA Astrophysics Data System (ADS)

Su, R.; Li, L.; Wang, Y. D.; Nie, Z. H.; Ren, Y.; Zhou, X.; Wang, J.

2018-05-01

The distribution of residual lattice strain as a function of depth were carefully investigated by synchrotron-based high energy X-ray diffraction (HEXRD) in TC11 titanium alloy after laser shock peening (LSP). The results presented big compressive residual lattice strains at surface and subsurface, then tensile residual lattice strains in deeper region, and finally close to zero lattice strains in further deep interior with no plastic deformation thereafter. These evolutions in residual lattice strains were attributed to the balance of direct load effect from laser shock wave and the derivative restriction force effect from surrounding material. Significant intergranular stress was evidenced in the processed sample. The intergranular stress exhibited the largest value at surface, and rapidly decreased with depth increase. The magnitude of intergranular stress was proportional to the severity of the plastic deformation caused by LSP. Two shocks generated larger intergranular stress than one shock.

Microstructure and Mechanical Properties of Porous Mullite

NASA Astrophysics Data System (ADS)

Hsiung, Chwan-Hai Harold

Mullite (3 Al2O3 : 2 SiO2) is a technologically important ceramic due to its thermal stability, corrosion resistance, and mechanical robustness. One variant, porous acicular mullite (ACM), has a unique needle-like microstructure and is the material platform for The Dow Chemical Company's diesel particulate filter AERIFY(TM). The investigation described herein focuses on the microstructure-mechanical property relationships in acicular mullites as well as those with traditional porous microstructures with the goal of illuminating the critical factors in determining their modulus, strength, and toughness. Mullites with traditional pore morphologies were made to serve as references via slipcasting of a kaolinite-alumina-starch slurry. The starch was burned out to leave behind a pore network, and the calcined body was then reaction-sintered at 1600C to form mullite. The samples had porosities of approximately 60%. Pore size and shape were altered by using different starch templates, and pore size was found to influence the stiffness and toughness. The ACM microstructure was varied along three parameters: total porosity, pore size, and needle size. Total porosity was found to dominate the mechanical behavior of ACM, while increases in needle and pore size increased the toughness at lower porosities. ACM was found to have much improved (˜130%) mechanical properties relative to its non-acicular counterpart at the same porosity. A second set of investigations studied the role of the intergranular glassy phase which wets the needle intersections of ACM. Removal of the glassy phase via an HF etch reduced the mechanical properties by ˜30%, highlighting the intergranular phase's importance to the enhanced mechanical properties of ACM. The composition of the glassy phase was altered by doping the ACM precursor with magnesium and neodymium. Magnesium doping resulted in ACM with greatly reduced fracture strength and toughness. Studies showed that the mechanical properties of the two doped intergranular glasses and their interfaces with mullite were quite similar. The reductions in strength and toughness were traced to differences in the ACM network structure and mass-distribution that are hypothesized to result from dopant-altered ACM nucleation and growth kinetics. X-ray computed tomography, a non-destructive 3-D imaging technique, played a key role in this work, enabling the measurement of needle diameters, quantification of the ACM structural network, and finite element analysis of ACM's mechanical response.

Miscibility of amorphous ZrO2-Al2O3 binary alloy

NASA Astrophysics Data System (ADS)

Zhao, C.; Richard, O.; Bender, H.; Caymax, M.; De Gendt, S.; Heyns, M.; Young, E.; Roebben, G.; Van Der Biest, O.; Haukka, S.

2002-04-01

Miscibility is a key factor for maintaining the homogeneity of the amorphous structure in a ZrO2-Al2O3 binary alloy high-k dielectric layer. In the present work, a ZrO2/Al2O3 laminate thin layer has been prepared by atomic layer chemical vapor deposition on a Si (100) wafer. This layer, with artificially induced inhomogeneity (lamination), enables one to study the change in homogeneity of the amorphous phase in the ZrO2/Al2O3 system during annealing. High temperature grazing incidence x-ray diffraction (HT-XRD) was used to investigate the change in intensity of the constructive interference peak of the x-ray beams which are reflected from the interfaces of ZrO2/Al2O3 laminae. The HT-XRD spectra show that the intensity of the peak decreases with an increase in the anneal temperature, and at 800 °C, the peak disappears. The same samples were annealed by a rapid thermal process (RTP) at temperatures between 700 and 1000 °C for 60 s. Room temperature XRD of the RTP annealed samples shows a similar decrease in peak intensity. Transmission electronic microscope images confirm that the laminate structure is destroyed by RTP anneals and, just below the crystallization onset temperature, a homogeneous amorphous ZrAlxOy phase forms. The results demonstrate that the two artificially separated phases, ZrO2 and Al2O3 laminae, tend to mix into a homogeneous amorphous phase before crystallization. This observation indicates that the thermal stability of ZrO2-Al2O3 amorphous phase is suitable for high-k applications.

High performance n-channel thin-film transistors with an amorphous phase C60 film on plastic substrate

NASA Astrophysics Data System (ADS)

Na, Jong H.; Kitamura, M.; Arakawa, Y.

2007-11-01

We fabricated high mobility, low voltage n-channel transistors on plastic substrates by combining an amorphous phase C60 film and a high dielectric constant gate insulator titanium silicon oxide (TiSiO2). The transistors exhibited high performance with a threshold voltage of 1.13V, an inverse subthreshold swing of 252mV/decade, and a field-effect mobility up to 1cm2/Vs at an operating voltage as low as 5V. The amorphous phase C60 films can be formed at room temperature, implying that this transistor is suitable for corresponding n-channel transistors in flexible organic logic devices.

Gold fillings unravel the vacancy role in the phase transition of GeTe

NASA Astrophysics Data System (ADS)

Feng, Jinlong; Xu, Meng; Wang, Xiaojie; Lin, Qi; Cheng, Xiaomin; Xu, Ming; Tong, Hao; Miao, Xiangshui

2018-02-01

Phase change memory (PCM) is an important candidate for future memory devices. The crystalline phase of PCM materials contains abundant intrinsic vacancies, which plays an important role in the rapid phase transition upon memory switching. However, few experimental efforts have been invested to study these invisible entities. In this work, Au dopants are alloyed into the crystalline GeTe to fill the intrinsic Ge vacancies so that the role of these vacancies in the amorphization of GeTe can be indirectly studied. As a result, the reduction of Ge vacancies induced by Au dopants hampers the amorphization of GeTe as the activation energy of this process becomes higher. This is because the vacancy-interrupted lattice can be "repaired" by Au dopants with the recovery of bond connectivity. Our results demonstrate the importance of vacancies in the phase transition of chalcogenides, and we employ the percolation theory to explain the impact of these intrinsic defects on this vacancy-ridden crystal quantitatively. Specifically, the threshold of amorphization increases with the decrease in vacancies. The understanding of the vacancy effect sheds light on the long-standing puzzle of the mechanism of ultra-fast phase transition in PCMs. It also paves the way for designing low-power-consumption electronic devices by reducing the threshold of amorphization in chalcogenides.

Structural transition and enhanced phase transition properties of Se doped Ge2Sb2Te5 alloys

NASA Astrophysics Data System (ADS)

Vinod, E. M.; Ramesh, K.; Sangunni, K. S.

2015-01-01

Amorphous Ge2Sb2Te5 (GST) alloy, upon heating crystallize to a metastable NaCl structure around 150°C and then to a stable hexagonal structure at high temperatures (>=250°C). It has been generally understood that the phase change takes place between amorphous and the metastable NaCl structure and not between the amorphous and the stable hexagonal phase. In the present work, it is observed that the thermally evaporated (GST)1-xSex thin films (0 <= x <= 0.50) crystallize directly to the stable hexagonal structure for x >= 0.10, when annealed at temperatures >= 150°C. The intermediate NaCl structure has been observed only for x < 0.10. Chemically ordered network of GST is largely modified for x >= 0.10. Resistance, thermal stability and threshold voltage of the films are found to increase with the increase of Se. The contrast in electrical resistivity between the amorphous and crystalline phases is about 6 orders of magnitude. The increase in Se shifts the absorption edge to lower wavelength and the band gap widens from 0.63 to 1.05 eV. Higher resistance ratio, higher crystallization temperature, direct transition to the stable phase indicate that (GST)1-xSex films are better candidates for phase change memory applications.

Local structure of amorphous Ag5In5Sb60Te30 and In3SbTe2 phase change materials revealed by X-ray photoelectron and Raman spectroscopic studies

NASA Astrophysics Data System (ADS)

Sahu, Smriti; Manivannan, Anbarasu; Shaik, Habibuddin; Mohan Rao, G.

2017-07-01

Reversible switching between highly resistive (binary "0") amorphous phase and low resistive (binary "1") crystalline phase of chalcogenide-based Phase Change Materials is accredited for the development of next generation high-speed, non-volatile, data storage applications. The doped Sb-Te based materials have shown enhanced electrical/optical properties, compared to Ge-Sb-Te family for high-speed memory devices. We report here the local atomic structure of as-deposited amorphous Ag5In5Sb60Te30 (AIST) and In3SbTe2 (IST) phase change materials using X-ray photoelectron and Raman spectroscopic studies. Although AIST and IST materials show identical crystallization behavior, they differ distinctly in their crystallization temperatures. Our experimental results demonstrate that the local environment of In remains identical in the amorphous phase of both AIST and IST material, irrespective of its atomic fraction. In bonds with Sb (˜44%) and Te (˜56%), thereby forming the primary matrix in IST with a very few Sb-Te bonds. Sb2Te constructs the base matrix for AIST (˜63%) along with few Sb-Sb bonds. Furthermore, an interesting assimilation of the role of small-scale dopants such as Ag and In in AIST, reveals rare bonds between themselves, while showing selective substitution in the vicinity of Sb and Te. This results in increased electronegativity difference, and consequently, the bond strength is recognized as the factor rendering stability in amorphous AIST.

Quasi-equilibrium size distribution of subcritical nuclei in amorphous phase change AgIn-Sb2Te

NASA Astrophysics Data System (ADS)

Darmawikarta, Kristof; Lee, Bong-Sub; Shelby, Robert M.; Raoux, Simone; Bishop, Stephen G.; Abelson, John R.

2013-07-01

We investigate the effect of low temperature annealing or of extended storage at room temperature on the subsequent nucleation behavior of amorphous AgIn-incorporated Sb2Te (AIST), a material for phase change memories. Time-resolved reflectivity measurements during pulsed laser crystallization reveal the rates of solid-phase transformation, while fluctuation transmission electron microscopy detects the nanoscale order in the amorphous phase prior to crystallization. The nanoscale order is postulated to consist of subcritical nuclei that coarsen upon annealing at temperatures ranging from 25 °C (for months) or 100 °C (for hours). Samples that have been annealed remain fully amorphous as evaluated by conventional diffraction experiments. Shorter nucleation times are consistently associated with the observation of increased nanoscale order. The effect of annealing is observed to saturate: there is no further reduction in nucleation time or increase in nanoscale order for annealing at 100 °C beyond three hours. This result supports the general prediction of classical nucleation theory that the size distribution of subcritical nuclei increases from the as-deposited state to a quasi-equilibrium.

Impact of polymers on the crystallization and phase transition kinetics of amorphous nifedipine during dissolution in aqueous media.

PubMed

Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2014-10-06

The commercial and clinical success of amorphous solid dispersions (ASD) in overcoming the low bioavailability of poorly soluble molecules has generated momentum among pharmaceutical scientists to advance the fundamental understanding of these complex systems. A major limitation of these formulations stems from the propensity of amorphous solids to crystallize upon exposure to aqueous media. This study was specifically focused on developing analytical techniques to evaluate the impact of polymers on the crystallization behavior during dissolution, which is critical in designing effective amorphous formulations. In the study, the crystallization and polymorphic conversions of a model compound, nifedipine, were explored in the absence and presence of polyvinylpyrrolidone (PVP), hydroxypropylmethyl cellulose (HPMC), and HPMC-acetate succinate (HPMC-AS). A combination of analytical approaches including Raman spectroscopy, polarized light microscopy, and chemometric techniques such as multivariate curve resolution (MCR) were used to evaluate the kinetics of crystallization and polymorphic transitions as well as to identify the primary route of crystallization, i.e., whether crystallization took place in the dissolving solid matrix or from the supersaturated solutions generated during dissolution. Pure amorphous nifedipine, when exposed to aqueous media, was found to crystallize rapidly from the amorphous matrix, even when polymers were present in the dissolution medium. Matrix crystallization was avoided when amorphous solid dispersions were prepared, however, crystallization from the solution phase was rapid. MCR was found to be an excellent data processing technique to deconvolute the complex phase transition behavior of nifedipine.

Characterization of carbon ion implantation induced graded microstructure and phase transformation in stainless steel

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

Feng, Kai; Wang, Yibo; Li, Zhuguo, E-mail: lizg@sjtu.edu.cn

Austenitic stainless steel 316L is ion implanted by carbon with implantation fluences of 1.2 × 10{sup 17} ions-cm{sup −} {sup 2}, 2.4 × 10{sup 17} ions-cm{sup −} {sup 2}, and 4.8 × 10{sup 17} ions-cm{sup −} {sup 2}. The ion implantation induced graded microstructure and phase transformation in stainless steel is investigated by X-ray diffraction, X-ray photoelectron spectroscopy and high resolution transmission electron microscopy. The corrosion resistance is evaluated by potentiodynamic test. It is found that the initial phase is austenite with a small amount of ferrite. After low fluence carbon ion implantation, an amorphous layer and ferrite phase enrichedmore » region underneath are formed. Nanophase particles precipitate from the amorphous layer due to energy minimization and irradiation at larger ion implantation fluence. The morphology of the precipitated nanophase particles changes from circular to dumbbell-like with increasing implantation fluence. The corrosion resistance of stainless steel is enhanced by the formation of amorphous layer and graphitic solid state carbon after carbon ion implantation. - Highlights: • Carbon implantation leads to phase transformation from austenite to ferrite. • The passive film on SS316L becomes thinner after carbon ion implantation. • An amorphous layer is formed by carbon ion implantation. • Nanophase precipitate from amorphous layer at higher ion implantation fluence. • Corrosion resistance of SS316L is improved by carbon implantation.« less

Experimental study of the polyamorphism of water. I. The isobaric transitions from amorphous ices to LDA at 4 MPa.

PubMed

Handle, Philip H; Loerting, Thomas

2018-03-28

The existence of more than one solid amorphous state of water is an extraordinary feature. Since polyamorphism might be connected to the liquid-liquid critical point hypothesis, it is particularly important to study the relations amongst the different amorphous ices. Here we study the polyamorphic transformations of several high pressure amorphous ices to low-density amorphous ice (LDA) at 4 MPa by isobaric heating utilising in situ volumetry and ex situ X-ray diffraction. We find that very-high density amorphous ice (VHDA) and unannealed high density amorphous ice (HDA) show significant relaxation before transforming to LDA, whereby VHDA is seen to relax toward HDA. By contrast, expanded HDA shows almost no relaxation prior to the transformation. The transition to LDA itself obeys criteria for a first-order-like transition in all cases. In the case of VHDA, even macroscopic phase separation is observed. These findings suggest that HDA and LDA are two clearly distinct polyamorphs. We further present evidence that HDA reaches the metastable equilibrium at 140 K and 0.1 GPa but only comes close to that at 140 K and 0.2 GPa. The most important is the path independence of the amorphous phase reached at 140 K and 0.1 GPa.

Pressure-induced amorphization in single-crystal Ta2O5 nanowires: a kinetic mechanism and improved electrical conductivity.

PubMed

Lü, Xujie; Hu, Qingyang; Yang, Wenge; Bai, Ligang; Sheng, Howard; Wang, Lin; Huang, Fuqiang; Wen, Jianguo; Miller, Dean J; Zhao, Yusheng

2013-09-18

Pressure-induced amorphization (PIA) in single-crystal Ta2O5 nanowires is observed at 19 GPa, and the obtained amorphous Ta2O5 nanowires show significant improvement in electrical conductivity. The phase transition process is unveiled by monitoring structural evolution with in situ synchrotron X-ray diffraction, pair distribution function, Raman spectroscopy, and transmission electron microscopy. The first principles calculations reveal the phonon modes softening during compression at particular bonds, and the analysis on the electron localization function also shows bond strength weakening at the same positions. On the basis of the experimental and theoretical results, a kinetic PIA mechanism is proposed and demonstrated systematically that amorphization is initiated by the disruption of connectivity between polyhedra (TaO6 octahedra or TaO7 bipyramids) at the particular weak-bonding positions along the a axis in the unit cell. The one-dimensional morphology is well-preserved for the pressure-induced amorphous Ta2O5, and the electrical conductivity is improved by an order of magnitude compared to traditional amorphous forms. Such pressure-induced amorphous nanomaterials with unique properties surpassing those in either crystalline or conventional amorphous phases hold great promise for numerous applications in the future.

Experimental study of the polyamorphism of water. I. The isobaric transitions from amorphous ices to LDA at 4 MPa

NASA Astrophysics Data System (ADS)

Handle, Philip H.; Loerting, Thomas

2018-03-01

The existence of more than one solid amorphous state of water is an extraordinary feature. Since polyamorphism might be connected to the liquid-liquid critical point hypothesis, it is particularly important to study the relations amongst the different amorphous ices. Here we study the polyamorphic transformations of several high pressure amorphous ices to low-density amorphous ice (LDA) at 4 MPa by isobaric heating utilising in situ volumetry and ex situ X-ray diffraction. We find that very-high density amorphous ice (VHDA) and unannealed high density amorphous ice (HDA) show significant relaxation before transforming to LDA, whereby VHDA is seen to relax toward HDA. By contrast, expanded HDA shows almost no relaxation prior to the transformation. The transition to LDA itself obeys criteria for a first-order-like transition in all cases. In the case of VHDA, even macroscopic phase separation is observed. These findings suggest that HDA and LDA are two clearly distinct polyamorphs. We further present evidence that HDA reaches the metastable equilibrium at 140 K and 0.1 GPa but only comes close to that at 140 K and 0.2 GPa. The most important is the path independence of the amorphous phase reached at 140 K and 0.1 GPa.

Pressure-induced amorphization of YVO₄:Eu³⁺ nanoboxes.

PubMed

Ruiz-Fuertes, J; Gomis, O; León-Luis, S F; Schrodt, N; Manjón, F J; Ray, S; Santamaría-Pérez, D; Sans, J A; Ortiz, H M; Errandonea, D; Ferrer-Roca, C; Segura, A; Martínez-García, D; Lavín, V; Rodríguez-Mendoza, U R; Muñoz, A

2016-01-15

A structural transformation from the zircon-type structure to an amorphous phase has been found in YVO4:Eu(3+) nanoboxes at high pressures above 12.7 GPa by means of x-ray diffraction measurements. However, the pair distribution function of the high-pressure phase shows that the local structure of the amorphous phase is similar to the scheelite-type YVO4. These results are confirmed both by Raman spectroscopy and Eu(3+) photoluminescence which detect the phase transition to a scheelite-type structure at 10.1 and 9.1 GPa, respectively. The irreversibility of the phase transition is observed with the three techniques after a maximum pressure in the upstroke of around 20 GPa. The existence of two (5)D0-->(7)F0 photoluminescence peaks confirms the existence of two local environments for Eu(3+), at least for the low-pressure phase. One environment is the expected for substituting Y(3+) and the other is likely a disordered environment possibly found at the surface of the nanoboxes.

Second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass.

PubMed

Cao, Q P; Li, J F; Zhang, P N; Horsewell, A; Jiang, J Z; Zhou, Y H

2007-06-20

The second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass was investigated by differential scanning calorimetry and x-ray diffractometry. The difference of the Gibbs free energies between the amorphous phase and the crystalline products during the transformation is estimated to be about 2.46 kJ mol(-1) at 753 K, much smaller than the 61 kJ mol(-1) obtained assuming that it is a polymorphic transformation. It was revealed that the phase transformation occurs through a eutectic crystallization of Cu(51)Zr(14) and Cu(2)TiZr, having an effective activation energy of the order of 400 kJ mol(-1). The average Avrami exponent n is about 2.0, indicating that the crystallization is diffusion controlled.

Morphological analysis of GeTe in inline phase change switches

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

King, Matthew R., E-mail: matthew.king2@ngc.com; Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695; El-Hinnawy, Nabil

2015-09-07

Crystallization and amorphization phenomena in indirectly heated phase change material-based devices were investigated. Scanning transmission electron microscopy was utilized to explore GeTe phase transition processes in the context of the unique inline phase change switch (IPCS) architecture. A monolithically integrated thin film heating element successfully converted GeTe to ON and OFF states. Device cycling prompted the formation of an active area which sustains the majority of structural changes during pulsing. A transition region on both sides of the active area consisting of polycrystalline GeTe and small nuclei (<15 nm) in an amorphous matrix was also observed. The switching mechanism, determined bymore » variations in pulsing parameters, was shown to be predominantly growth-driven. A preliminary model for crystallization and amorphization in IPCS devices is presented.« less

Quantitative Phase Analysis of Plasma-Treated High-Silica Materials

NASA Astrophysics Data System (ADS)

Kosmachev, P. V.; Abzaev, Yu. A.; Vlasov, V. A.

2018-06-01

The paper presents the X-ray diffraction (XRD) analysis of the crystal structure of SiO2 in two modifications, namely quartzite and quartz sand before and after plasma treatment. Plasma treatment enables the raw material to melt and evaporate after which the material quenches and condenses to form nanoparticles. The Rietveld refinement method is used to identify the lattice parameters of SiO2 phases. It is found that after plasma treatment SiO2 oxides are in the amorphous state, which are modeled within the microcanonical ensemble. Experiments show that amorphous phases are stable, and model X-ray reflection intensities approximate the experimental XRD patterns with fine precision. Within the modeling, full information is obtained for SiO2 crystalline and amorphous phases, which includes atom arrangement, structural parameters, atomic population of silicon and oxygen atoms in lattice sites.

Overview of the amorphous precursor phase strategy in biomineralization

NASA Astrophysics Data System (ADS)

Weiner, Steve; Mahamid, Julia; Politi, Yael; Ma, Yurong; Addadi, Lia

2009-06-01

It was assumed for a long time that organisms produce minerals directly from a saturated solution. A few exceptions were known, including the well documented mineralized teeth of the chiton. In 1997 it was demon-strated that sea urchin larvae form their calcitic spicules by first depositing a highly unstable mineral phase called amorphous calcium carbonate. This strategy has since been shown to be used by animals from other phyla and for both aragonite and calcite. Recent evidence shows that vertebrate bone mineral may also be formed via a precursor phase of amorphous calcium carbonate. This strategy thus appears to be widespread. The challenge now is to understand the mechanisms by which these unstable phases are initially formed, how they are temporarily stabilized and how they are destabilized and transform into a crystalline mature product.

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.

The relation between high-density and very-high-density amorphous ice.

PubMed

Loerting, Thomas; Salzmann, Christoph G; Winkel, Katrin; Mayer, Erwin

2006-06-28

The exact nature of the relationship between high-density (HDA) and very-high-density (VHDA) amorphous ice is unknown at present. Here we review the relation between HDA and VHDA, concentrating on experimental aspects and discuss these with respect to the relation between low-density amorphous ice (LDA) and HDA. On compressing LDA at 125 K up to 1.5 GPa, two distinct density steps are observable in the pressure-density curves which correspond to the LDA --> HDA and HDA --> VHDA conversion. This stepwise formation process LDA --> HDA --> VHDA at 125 K is the first unambiguous observation of a stepwise amorphous-amorphous-amorphous transformation sequence. Density values of amorphous ice obtained in situ between 0.3 and 1.9 GPa on isobaric heating up to the temperatures of crystallization show a pronounced change of slope at ca. 0.8 GPa which could indicate formation of a distinct phase. We infer that the relation between HDA and VHDA is very similar to that between LDA and HDA except for a higher activation barrier between the former. We further discuss the two options of thermodynamic phase transition versus kinetic densification for the HDA --> VHDA conversion.

Demonstration of thin film pair distribution function analysis (tfPDF) for the study of local structure in amorphous and crystalline thin films

DOE PAGES

Jensen, K. M.Ø.; Blichfeld, A. B.; Bauers, S. R.; ...

2015-07-05

By means of normal incidence, high flux and high energy x-rays, we have obtained total scattering data for Pair Distribution Function (PDF) analysis from thin films (tf), suitable for local structure analysis. By using amorphous substrates as support for the films, the standard Rapid Acquisition PDF setup can be applied and the scattering signal from the film can be isolated from the total scattering data through subtraction of an independently measured background signal. No angular corrections to the data are needed, as would be the case for grazing incidence measurements. We illustrate the ‘tfPDF’ method through studies of as depositedmore » (i.e. amorphous) and crystalline FeSb 3 films, where the local structure analysis gives insight into the stabilization of the metastable skutterudite FeSb 3 phase. The films were prepared by depositing ultra-thin alternating layers of Fe and Sb, which interdiffuse and after annealing crystallize to form the FeSb 3 structure. The tfPDF data show that the amorphous precursor phase consists of corner-sharing FeSb 6 octahedra with motifs highly resembling the local structure in crystalline FeSb 3. Analysis of the amorphous structure allows predicting whether the final crystalline product will form the FeSb 3 phase with or without excess Sb present. The study thus illustrates how analysis of the local structure in amorphous precursor films can help to understand crystallization processes of metastable phases and opens for a range of new local structure studies of thin films.« less

Demonstration of thin film pair distribution function analysis (tfPDF) for the study of local structure in amorphous and crystalline thin films

PubMed Central

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

2015-01-01

By means of normal-incidence, high-flux and high-energy X-rays, total scattering data for pair distribution function (PDF) analysis have been obtained from thin films (tf), suitable for local structure analysis. By using amorphous substrates as support for the films, the standard Rapid Acquisition PDF setup can be applied and the scattering signal from the film can be isolated from the total scattering data through subtraction of an independently measured background signal. No angular corrections to the data are needed, as would be the case for grazing incidence measurements. The ‘tfPDF’ method is illustrated through studies of as-deposited (i.e. amorphous) and crystalline FeSb3 films, where the local structure analysis gives insight into the stabilization of the metastable skutterudite FeSb3 phase. The films were prepared by depositing ultra-thin alternating layers of Fe and Sb, which interdiffuse and after annealing crystallize to form the FeSb3 structure. The tfPDF data show that the amorphous precursor phase consists of corner-sharing FeSb6 octahedra with motifs highly resembling the local structure in crystalline FeSb3. Analysis of the amorphous structure allows the prediction of whether the final crystalline product will form the FeSb3 phase with or without excess Sb present. The study thus illustrates how analysis of the local structure in amorphous precursor films can help to understand crystallization processes of metastable phases and opens for a range of new local structure studies of thin films. PMID:26306190

Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

PubMed

Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel

2015-06-01

Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of Secondary Phase Precipitation on the Corrosion Behavior of Duplex Stainless Steels.

PubMed

Chan, Kai Wang; Tjong, Sie Chin

2014-07-22

Duplex stainless steels (DSSs) with austenitic and ferritic phases have been increasingly used for many industrial applications due to their good mechanical properties and corrosion resistance in acidic, caustic and marine environments. However, DSSs are susceptible to intergranular, pitting and stress corrosion in corrosive environments due to the formation of secondary phases. Such phases are induced in DSSs during the fabrication, improper heat treatment, welding process and prolonged exposure to high temperatures during their service lives. These include the precipitation of sigma and chi phases at 700-900 °C and spinodal decomposition of ferritic grains into Cr-rich and Cr-poor phases at 350-550 °C, respectively. This article gives the state-of the-art review on the microstructural evolution of secondary phase formation and their effects on the corrosion behavior of DSSs.

Co-based amorphous thin films on silicon with soft magnetic properties

NASA Astrophysics Data System (ADS)

Masood, Ansar; McCloskey, P.; Mathúna, Cian Ó.; Kulkarni, S.

2018-05-01

The present work investigates the emergence of multiple modes in the high-frequency permeability spectrum of Co-Zr-Ta-B amorphous thin films. Amorphous thin films of different thicknesses (t=100-530 nm) were deposited by DC magnetron sputtering. Their static and dynamic soft magnetic properties were investigated to explore the presence of multi-magnetic phases in the films. A two-phase magnetic behavior of the thicker films (≥333 nm) was revealed by the in-plane hysteresis loops. Multiple resonance peaks were observed in the high-frequency permeability spectrum of the thicker films. The thickness dependent multiple resonance peaks below the main ferromagnetic resonance (FMR) can be attributed to the two-phase magnetic behaviors of the films.

Influence of the local structure in phase-change materials on their dielectric permittivity.

PubMed

Shportko, Kostiantyn V; Venger, Eugen F

2015-01-01

Ge-Sb-Te alloys, which belong to the phase-change materials, are promising materials for data storage and display and data visualization applications due to their unique properties. This includes a remarkable difference of their electrical and optical properties in the amorphous and crystalline state. Pronounced change of optical properties for Ge-Sb-Te alloys is linked to the different bonding types and different atomic arrangements in amorphous and crystalline states. The dielectric function of phase-change materials has been investigated in the far infrared (FIR) range. Phonons have been detected by FTIR spectroscopy. Difference of the dispersion of the dielectric permittivity of amorphous and crystalline samples is caused by different structures in different states which contribute to the dielectric permittivity.

Amorphization and reduction of thermal conductivity in porous silicon by irradiation with swift heavy ions

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

Newby, Pascal J.; Institut Interdisciplinaire d'Innovation Technologique; Canut, Bruno

2013-07-07

In this article, we demonstrate that the thermal conductivity of nanostructured porous silicon is reduced by amorphization and also that this amorphous phase in porous silicon can be created by swift (high-energy) heavy ion irradiation. Porous silicon samples with 41%-75% porosity are irradiated with 110 MeV uranium ions at six different fluences. Structural characterisation by micro-Raman spectroscopy and SEM imaging show that swift heavy ion irradiation causes the creation of an amorphous phase in porous Si but without suppressing its porous structure. We demonstrate that the amorphization of porous silicon is caused by electronic-regime interactions, which is the first timemore » such an effect is obtained in crystalline silicon with single-ion species. Furthermore, the impact on the thermal conductivity of porous silicon is studied by micro-Raman spectroscopy and scanning thermal microscopy. The creation of an amorphous phase in porous silicon leads to a reduction of its thermal conductivity, up to a factor of 3 compared to the non-irradiated sample. Therefore, this technique could be used to enhance the thermal insulation properties of porous Si. Finally, we show that this treatment can be combined with pre-oxidation at 300 Degree-Sign C, which is known to lower the thermal conductivity of porous Si, in order to obtain an even greater reduction.« less

Ultrafast time-resolved electron diffraction revealing the nonthermal dynamics of near-UV photoexcitation-induced amorphization in Ge2Sb2Te5.

PubMed

Hada, Masaki; Oba, Wataru; Kuwahara, Masashi; Katayama, Ikufumi; Saiki, Toshiharu; Takeda, Jun; Nakamura, Kazutaka G

2015-08-28

Because of their robust switching capability, chalcogenide glass materials have been used for a wide range of applications, including optical storages devices. These phase transitions are achieved by laser irradiation via thermal processes. Recent studies have suggested the potential of nonthermal phase transitions in the chalcogenide glass material Ge2Sb2Te5 triggered by ultrashort optical pulses; however, a detailed understanding of the amorphization and damage mechanisms governed by nonthermal processes is still lacking. Here we performed ultrafast time-resolved electron diffraction and single-shot optical pump-probe measurements followed by femtosecond near-ultraviolet pulse irradiation to study the structural dynamics of polycrystalline Ge2Sb2Te5. The experimental results present a nonthermal crystal-to-amorphous phase transition of Ge2Sb2Te5 initiated by the displacements of Ge atoms. Above the fluence threshold, we found that the permanent amorphization caused by multi-displacement effects is accompanied by a partial hexagonal crystallization.

Ultrafast time-resolved electron diffraction revealing the nonthermal dynamics of near-UV photoexcitation-induced amorphization in Ge2Sb2Te5

PubMed Central

Hada, Masaki; Oba, Wataru; Kuwahara, Masashi; Katayama, Ikufumi; Saiki, Toshiharu; Takeda, Jun; Nakamura, Kazutaka G.

2015-01-01

Because of their robust switching capability, chalcogenide glass materials have been used for a wide range of applications, including optical storages devices. These phase transitions are achieved by laser irradiation via thermal processes. Recent studies have suggested the potential of nonthermal phase transitions in the chalcogenide glass material Ge2Sb2Te5 triggered by ultrashort optical pulses; however, a detailed understanding of the amorphization and damage mechanisms governed by nonthermal processes is still lacking. Here we performed ultrafast time-resolved electron diffraction and single-shot optical pump-probe measurements followed by femtosecond near-ultraviolet pulse irradiation to study the structural dynamics of polycrystalline Ge2Sb2Te5. The experimental results present a nonthermal crystal-to-amorphous phase transition of Ge2Sb2Te5 initiated by the displacements of Ge atoms. Above the fluence threshold, we found that the permanent amorphization caused by multi-displacement effects is accompanied by a partial hexagonal crystallization. PMID:26314613

Fabrication of amorphous micro-ring arrays in crystalline silicon using ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Fuentes-Edfuf, Yasser; Garcia-Lechuga, Mario; Puerto, Daniel; Florian, Camilo; Garcia-Leis, Adianez; Sanchez-Cortes, Santiago; Solis, Javier; Siegel, Jan

2017-05-01

We demonstrate a simple way to fabricate amorphous micro-rings in crystalline silicon using direct laser writing. This method is based on the fact that the phase of a thin surface layer can be changed into the amorphous phase by irradiation with a few ultrashort laser pulses (800 nm wavelength and 100 fs duration). Surface-depressed amorphous rings with a central crystalline disk can be fabricated without the need for beam shaping, featuring attractive optical, topographical, and electrical properties. The underlying formation mechanism and phase change pathway have been investigated by means of fs-resolved microscopy, identifying fluence-dependent melting and solidification dynamics of the material as the responsible mechanism. We demonstrate that the lateral dimensions of the rings can be scaled and that the rings can be stitched together, forming extended arrays of structures not limited to annular shapes. This technique and the resulting structures may find applications in a variety of fields such as optics, nanoelectronics, and mechatronics.

Ultralow-power switching via defect engineering in germanium telluride phase-change memory devices.

PubMed

Nukala, Pavan; Lin, Chia-Chun; Composto, Russell; Agarwal, Ritesh

2016-01-25

Crystal-amorphous transformation achieved via the melt-quench pathway in phase-change memory involves fundamentally inefficient energy conversion events; and this translates to large switching current densities, responsible for chemical segregation and device degradation. Alternatively, introducing defects in the crystalline phase can engineer carrier localization effects enhancing carrier-lattice coupling; and this can efficiently extract work required to introduce bond distortions necessary for amorphization from input electrical energy. Here, by pre-inducing extended defects and thus carrier localization effects in crystalline GeTe via high-energy ion irradiation, we show tremendous improvement in amorphization current densities (0.13-0.6 MA cm(-2)) compared with the melt-quench strategy (∼50 MA cm(-2)). We show scaling behaviour and good reversibility on these devices, and explore several intermediate resistance states that are accessible during both amorphization and recrystallization pathways. Existence of multiple resistance states, along with ultralow-power switching and scaling capabilities, makes this approach promising in context of low-power memory and neuromorphic computation.

Ultralow-power switching via defect engineering in germanium telluride phase-change memory devices

PubMed Central

Nukala, Pavan; Lin, Chia-Chun; Composto, Russell; Agarwal, Ritesh

2016-01-01

Crystal–amorphous transformation achieved via the melt-quench pathway in phase-change memory involves fundamentally inefficient energy conversion events; and this translates to large switching current densities, responsible for chemical segregation and device degradation. Alternatively, introducing defects in the crystalline phase can engineer carrier localization effects enhancing carrier–lattice coupling; and this can efficiently extract work required to introduce bond distortions necessary for amorphization from input electrical energy. Here, by pre-inducing extended defects and thus carrier localization effects in crystalline GeTe via high-energy ion irradiation, we show tremendous improvement in amorphization current densities (0.13–0.6 MA cm−2) compared with the melt-quench strategy (∼50 MA cm−2). We show scaling behaviour and good reversibility on these devices, and explore several intermediate resistance states that are accessible during both amorphization and recrystallization pathways. Existence of multiple resistance states, along with ultralow-power switching and scaling capabilities, makes this approach promising in context of low-power memory and neuromorphic computation. PMID:26805748

The Structure of Liquid and Amorphous Hafnia.

PubMed

Gallington, Leighanne C; Ghadar, Yasaman; Skinner, Lawrie B; Weber, J K Richard; Ushakov, Sergey V; Navrotsky, Alexandra; Vazquez-Mayagoitia, Alvaro; Neuefeind, Joerg C; Stan, Marius; Low, John J; Benmore, Chris J

2017-11-10

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf-O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that show density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf-Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf-Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO 6,7 polyhedra resembling that observed in the monoclinic phase.

Formation of amorphous materials

DOEpatents

Johnson, William L.; Schwarz, Ricardo B.

1986-01-01

Metastable amorphous or fine crystalline materials are formed by solid state reactions by diffusion of a metallic component into a solid compound or by diffusion of a gas into an intermetallic compound. The invention can be practiced on layers of metals deposited on an amorphous substrate or by intermixing powders with nucleating seed granules. All that is required is that the diffusion of the first component into the second component be much faster than the self-diffusion of the first component. The method is practiced at a temperature below the temperature at which the amorphous phase transforms into one or more crystalline phases and near or below the temperature at which the ratio of the rate of diffusion of the first component to the rate of self-diffusion is at least 10.sup.4. This anomalous diffusion criteria is found in many binary, tertiary and higher ordered systems of alloys and appears to be found in all alloy systems that form amorphous materials by rapid quenching. The method of the invention can totally convert much larger dimensional materials to amorphous materials in practical periods of several hours or less.

The Structure of Liquid and Amorphous Hafnia

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

Gallington, Leighanne; Ghadar, Yasaman; Skinner, Lawrie

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf–O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that showmore » density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf–Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf–Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO 6,7 polyhedra resembling that observed in the monoclinic phase.« less

The Structure of Liquid and Amorphous Hafnia

DOE PAGES

Gallington, Leighanne; Ghadar, Yasaman; Skinner, Lawrie; ...

2017-11-10

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf–O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that showmore » density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf–Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf–Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO 6,7 polyhedra resembling that observed in the monoclinic phase.« less

Supramolecular structure, phase behavior and thermo-rheological properties of a poly (L-lactide-co-ε-caprolactone) statistical copolymer.

PubMed

Ugartemendia, Jone M; Muñoz, M E; Santamaria, A; Sarasua, J R

2015-08-01

PLAcoCL samples, both unaged, termed PLAcoCLu, and aged over time, PLAcoCLa, were prepared and analyzed to study the phase structure, morphology, and their evolution under non-quiescent conditions. X- ray diffraction, Differential Scanning Calorimetry and Atomic Force Microscopy were complemented with thermo-rheological measurements to reveal that PLAcoCL evolves over time from a single amorphous metastable state to a 3 phase system, made up of two compositionally different amorphous phases and a crystalline phase. The supramolecular arrangements developed during aging lead to a rheological complex behavior in the PLAcoCLa copolymer: Around Tt=131 °C thermo-rheological complexity and a peculiar chain mobility reduction were observed, but at T>Tt the thermo-rheological response of a homogeneous system was recorded. In comparison with the latter, the PLLA/PCL 70:30 physical blend counterpart showed double amorphous phase behavior at all temperatures, supporting the hypothesis that phase separation in the PLAcoCLa copolymer is caused by the crystallization of polylactide segment blocks during aging. Copyright © 2015 Elsevier Ltd. All rights reserved.

Defect-induced solid state amorphization of molecular crystals

NASA Astrophysics Data System (ADS)

Lei, Lei; Carvajal, Teresa; Koslowski, Marisol

2012-04-01

We investigate the process of mechanically induced amorphization in small molecule organic crystals under extensive deformation. In this work, we develop a model that describes the amorphization of molecular crystals, in which the plastic response is calculated with a phase field dislocation dynamics theory in four materials: acetaminophen, sucrose, γ-indomethacin, and aspirin. The model is able to predict the fraction of amorphous material generated in single crystals for a given applied stress. Our results show that γ-indomethacin and sucrose demonstrate large volume fractions of amorphous material after sufficient plastic deformation, while smaller amorphous volume fractions are predicted in acetaminophen and aspirin, in agreement with experimental observation.

Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase.

PubMed

Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia

2004-11-12

The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

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.

Nanoscale solely amorphous layer in silicon wafers induced by a newly developed diamond wheel

PubMed Central

Zhang, Zhenyu; Guo, Liangchao; Cui, Junfeng; Wang, Bo; Kang, Renke; Guo, Dongming

2016-01-01

Nanoscale solely amorphous layer is achieved in silicon (Si) wafers, using a developed diamond wheel with ceria, which is confirmed by high resolution transmission electron microscopy (HRTEM). This is different from previous reports of ultraprecision grinding, nanoindentation and nanoscratch, in which an amorphous layer at the top, followed by a crystalline damaged layer beneath. The thicknesses of amorphous layer are 43 and 48 nm at infeed rates of 8 and 15 μm/min, respectively, which is verified using HRTEM. Diamond-cubic Si-I phase is verified in Si wafers using selected area electron diffraction patterns, indicating the absence of high pressure phases. Ceria plays an important role in the diamond wheel for achieving ultrasmooth and bright surfaces using ultraprecision grinding. PMID:27734934

Solubility of crystalline organic compounds in high and low molecular weight amorphous matrices above and below the glass transition by zero enthalpy extrapolation.

PubMed

Amharar, Youness; Curtin, Vincent; Gallagher, Kieran H; Healy, Anne Marie

2014-09-10

Pharmaceutical applications which require knowledge of the solubility of a crystalline compound in an amorphous matrix are abundant in the literature. Several methods that allow the determination of such data have been reported, but so far have only been applicable to amorphous polymers above the glass transition of the resulting composites. The current work presents, for the first time, a reliable method for the determination of the solubility of crystalline pharmaceutical compounds in high and low molecular weight amorphous matrices at the glass transition and at room temperature (i.e. below the glass transition temperature), respectively. The solubilities of mannitol and indomethacin in polyvinyl pyrrolidone (PVP) K15 and PVP K25, respectively were measured at different temperatures. Mixtures of undissolved crystalline solute and saturated amorphous phase were obtained by annealing at a given temperature. The solubility at this temperature was then obtained by measuring the melting enthalpy of the crystalline phase, plotting it as a function of composition and extrapolating to zero enthalpy. This new method yielded results in accordance with the predictions reported in the literature. The method was also adapted for the measurement of the solubility of crystalline low molecular weight excipients in amorphous active pharmaceutical ingredients (APIs). The solubility of mannitol, glutaric acid and adipic acid in both indomethacin and sulfadimidine was experimentally determined and successfully compared with the difference between their respective calculated Hildebrand solubility parameters. As expected from the calculations, the dicarboxylic acids exhibited a high solubility in both amorphous indomethacin and sulfadimidine, whereas mannitol was almost insoluble in the same amorphous phases at room temperature. This work constitutes the first report of the methodology for determining an experimentally measured solubility for a low molecular weight crystalline solute in a low molecular weight amorphous matrix. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesizing skyrmion bound pairs in Fe-Gd thin films

DOE PAGES

Lee, J. C. T.; Chess, J. J.; Montoya, S. A.; ...

2016-07-11

Here, we show that properly engineered amorphous Fe-Gd alloy thin films with perpendicular magnetic anisotropy exhibit bound pairs of like-polarity, opposite helicity skyrmions at room temperature. Magnetic mirror symmetry planes present in the stripe phase, instead of chiral exchange, determine the internal skyrmion structure and the net achirality of the skyrmion phase. Our study shows that stripe domain engineering in amorphous alloy thin films may enable the creation of skyrmion phases with technologically desirable properties.

Microstructural Evolution and Mechanical Properties of Nanointermetallic Phase Dispersed Al65Cu20Ti15 Amorphous Matrix Composite Synthesized by Mechanical Alloying and Hot Isostatic Pressing

NASA Astrophysics Data System (ADS)

Roy, D.; Mitra, R.; Ojo, O. A.; Lojkowski, W.; Manna, I.

2011-08-01

The structure and mechanical properties of nanocrystalline intermetallic phase dispersed amorphous matrix composite prepared by hot isostatic pressing (HIP) of mechanically alloyed Al65Cu20Ti15 amorphous powder in the temperature range 573 K to 873 K (300 °C to 600 °C) with 1.2 GPa pressure were studied. Phase identification by X-ray diffraction (XRD) and microstructural investigation by transmission electron microscopy confirmed that sintering in this temperature range led to partial crystallization of the amorphous powder. The microstructures of the consolidated composites were found to have nanocrystalline intermetallic precipitates of Al5CuTi2, Al3Ti, AlCu, Al2Cu, and Al4Cu9 dispersed in amorphous matrix. An optimum combination of density (3.73 Mg/m3), hardness (8.96 GPa), compressive strength (1650 MPa), shear strength (850 MPa), and Young's modulus (182 GPa) were obtained in the composite hot isostatically pressed ("hipped") at 773 K (500 °C). Furthermore, these results were compared with those from earlier studies based on conventional sintering (CCS), high pressure sintering (HPS), and pulse plasma sintering (PPS). HIP appears to be the most preferred process for achieving an optimum combination of density and mechanical properties in amorphous-nanocrystalline intermetallic composites at temperatures ≤773 K (500 °C), while HPS is most suited for bulk amorphous alloys. Both density and volume fraction of intermetallic dispersoids were found to influence the mechanical properties of the composites.

Formation of ultrathin Ni germanides: solid-phase reaction, morphology and texture

NASA Astrophysics Data System (ADS)

van Stiphout, K.; Geenen, F. A.; De Schutter, B.; Santos, N. M.; Miranda, S. M. C.; Joly, V.; Detavernier, C.; Pereira, L. M. C.; Temst, K.; Vantomme, A.

2017-11-01

The solid-phase reaction of ultrathin (⩽10 nm) Ni films with different Ge substrates (single-crystalline (1 0 0), polycrystalline, and amorphous) was studied. As thickness goes down, thin film texture becomes a dominant factor in both the film’s phase formation and morphological evolution. As a consequence, certain metastable microstructures are epitaxially stabilized on crystalline substrates, such as the ɛ-Ni5Ge3 phase or a strained NiGe crystal structure on the single-crystalline substrates. Similarly, the destabilizing effect of axiotaxial texture on the film’s morphology becomes more pronounced as film thicknesses become smaller. These effects are contrasted by the evolution of germanide films on amorphous substrates, on which neither epitaxy nor axiotaxy can form, i.e. none of the (de)stabilizing effects of texture are observed. The crystallization of such amorphous substrates however, drives the film breakup.

Reversible switching between pressure-induced amorphization and thermal-driven recrystallization in VO2(B) nanosheets

PubMed Central

Wang, Yonggang; Zhu, Jinlong; Yang, Wenge; Wen, Ting; Pravica, Michael; Liu, Zhenxian; Hou, Mingqiang; Fei, Yingwei; Kang, Lei; Lin, Zheshuai; Jin, Changqing; Zhao, Yusheng

2016-01-01

Pressure-induced amorphization (PIA) and thermal-driven recrystallization have been observed in many crystalline materials. However, controllable switching between PIA and a metastable phase has not been described yet, due to the challenge to establish feasible switching methods to control the pressure and temperature precisely. Here, we demonstrate a reversible switching between PIA and thermally-driven recrystallization of VO2(B) nanosheets. Comprehensive in situ experiments are performed to establish the precise conditions of the reversible phase transformations, which are normally hindered but occur with stimuli beyond the energy barrier. Spectral evidence and theoretical calculations reveal the pressure–structure relationship and the role of flexible VOx polyhedra in the structural switching process. Anomalous resistivity evolution and the participation of spin in the reversible phase transition are observed for the first time. Our findings have significant implications for the design of phase switching devices and the exploration of hidden amorphous materials. PMID:27426219

Reversible switching between pressure-induced amorphization and thermal-driven recrystallization in VO2(B) nanosheets.

PubMed

Wang, Yonggang; Zhu, Jinlong; Yang, Wenge; Wen, Ting; Pravica, Michael; Liu, Zhenxian; Hou, Mingqiang; Fei, Yingwei; Kang, Lei; Lin, Zheshuai; Jin, Changqing; Zhao, Yusheng

2016-07-18

Pressure-induced amorphization (PIA) and thermal-driven recrystallization have been observed in many crystalline materials. However, controllable switching between PIA and a metastable phase has not been described yet, due to the challenge to establish feasible switching methods to control the pressure and temperature precisely. Here, we demonstrate a reversible switching between PIA and thermally-driven recrystallization of VO2(B) nanosheets. Comprehensive in situ experiments are performed to establish the precise conditions of the reversible phase transformations, which are normally hindered but occur with stimuli beyond the energy barrier. Spectral evidence and theoretical calculations reveal the pressure-structure relationship and the role of flexible VOx polyhedra in the structural switching process. Anomalous resistivity evolution and the participation of spin in the reversible phase transition are observed for the first time. Our findings have significant implications for the design of phase switching devices and the exploration of hidden amorphous materials.

Effect of Se substitution on the phase change properties of Ge2Sb2Te5

NASA Astrophysics Data System (ADS)

Shekhawat, Roopali; Rangappa, Ramanna; Gopal, E. S. R.; Ramesh, K.

2018-05-01

Ge2Sb2Te5 popularly known as GST is being explored for non-volatile phase change random access memory(PCRAM) applications. Under high electric field, thin films of amorphous GST undergo a phase change from amorphous to crystalline with a high contrast in electrical resistivity (about 103). The phase change is between amorphous and metastable NaCl structure occurs at about 150°C and not to the stable hexagonal phase which occurs at a high temperature (> 250 °C). In GST, about 50 % of Te substituted by Se (Ge2Sb2Te2.5Se2.5) is found to increase the contrast in electrical resistivity by 7 orders of magnitude (about 4 orders of magnitude higher than GST). The phase transition in Se added GST also found to be between amorphous and the stable hexagonal structure. The threshold voltage at which the Ge2Sb2Te2.5Se2.5 switches to the high conducting state increases to 9V as compared to 2V in GST. Interestingly, the threshold current decrease to 1mA as compared to 1.8mA in GST indicating the Se substitution reduces the power needed for switching between the low and high conducting states. The reduction in power needed for phase change, high contrast in electrical resistivity with high thermal stability makes Ge2Sb2Te2.5Se2.5 as a better candidate for PCRAM.

ESR Measurement Of Crystallinity In Semicrystalline Polymers

NASA Technical Reports Server (NTRS)

Kim, Soon Sam; Tsay, Fun-Dow

1989-01-01

Photogenerated free radicals decay at different rates in crystalline and amorphous phases. Degree of crystallinity in polymer having both crystalline and amorphous phases measured indirectly by technique based in part on electron-spin-resonance (ESR) spectroscopy. Accuracy of crystallinity determined by new technique equals or exceeds similar determinations by differential scanning calorimetry, wide-angle x-ray scattering, or measurement of density.

First-principles study of the amorphous In3SbTe2 phase change compound

NASA Astrophysics Data System (ADS)

Los, Jan H.; Kühne, Thomas D.; Gabardi, Silvia; Bernasconi, Marco

2013-11-01

Ab initio molecular dynamics simulations based on density functional theory were performed to generate amorphous models of the phase change compound In3SbTe2 by quenching from the melt. In-Sb and In-Te are the most abundant bonds with only a minor fraction of Sb-Te bonds. The bonding geometry in the amorphous phase is, however, strongly dependent on the density in the range 6.448-5.75 g/cm3 that we investigated. While at high density the bonding geometry of In atoms is mostly octahedral-like as in the cubic crystalline phase of the ternary compound In3SbTe2, at low density we observed a sizable fraction of tetrahedral-like geometries similar to those present in the crystalline phase of the two binary compounds InTe and InSb that the ternary system can be thought to be made of. We show that the different ratio between octahedral-like and tetrahedral-like bonding geometries has fingerprints in the optical and vibrational spectra.

Atom-Level Understanding of the Sodiation Process in Silicon Anode Material.

PubMed

Jung, Sung Chul; Jung, Dae Soo; Choi, Jang Wook; Han, Young-Kyu

2014-04-03

Despite the exceptionally large capacities in Li ion batteries, Si has been considered inappropriate for applications in Na ion batteries. We report an atomic-level study on the applicability of a Si anode in Na ion batteries using ab initio molecular dynamics simulations. While crystalline Si is not suitable for alloying with Na atoms, amorphous Si can accommodate 0.76 Na atoms per Si atom, corresponding to a specific capacity of 725 mA h g(-1). Bader charge analyses reveal that the sodiation of an amorphous Si electrode continues until before the local Na-rich clusters containing neutral Na atoms are formed. The amorphous Na0.76Si phase undergoes a volume expansion of 114% and shows a Na diffusivity of 7 × 10(-10) cm(2) s(-1) at room temperature. Overall, the amorphous Si phase turns out quite attractive in performance compared to other alloy-type anode materials. This work suggests that amorphous Si might be a competitive candidate for Na ion battery anodes.

Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass

PubMed Central

Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

2015-01-01

In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant. PMID:26658671

Remarkably stable amorphous metal oxide grown on Zr-Cu-Be metallic glass.

PubMed

Lim, Ka Ram; Kim, Chang Eun; Yun, Young Su; Kim, Won Tae; Soon, Aloysius; Kim, Do Hyang

2015-12-14

In the present study, we investigated the role of an aliovalent dopant upon stabilizing the amorphous oxide film. We added beryllium into the Zr50Cu50 metallic glass system, and found that the amorphous oxide layer of Be-rich phase can be stabilized even at elevated temperature above Tg of the glass matrix. The thermal stability of the amorphous oxide layer is substantially enhanced due to Be addition. As confirmed by high-temperature cross-section HR-TEM, fully disordered Be-added amorphous layer is observed, while the rapid crystallization is observed without Be. To understand the role of Be, we employed ab-initio molecular dynamics to compare the mobility of ions with/without Be dopant, and propose a disordered model where Be dopant occupies Zr vacancy and induces structural disorder to the amorphous phase. We find that the oxygen mobility is slightly suppressed due to Be dopant, and Be mobility is unexpectedly lower than that of oxygen, which we attribute to the aliovalent nature of Be dopant whose diffusion always accompany multiple counter-diffusion of other ions. Here, we explain the origin of superior thermal stability of amorphous oxide film in terms of enhanced structural disorder and suppressed ionic mobility due to the aliovalent dopant.

Amorphous Ni(OH)2/CQDs microspheres for highly sensitive non-enzymatic glucose detection prepared via CQDs induced aggregation process

NASA Astrophysics Data System (ADS)

Zhu, Jiajie; Yin, Haoyong; Cui, Zhenzhen; Qin, Dongyu; Gong, Jianying; Nie, Qiulin

2017-10-01

Non-enzymatic electrochemical sensors for the detection of glucose were designed based on amorphous Ni(OH)2/CQDs microspheres. The amorphous Ni(OH)2/CQDs microspheres were prepared by a CQDs assistant crystallization inhibition process. The morphologies and composition of the microspheres were characterized by SEM, TEM, XRD, EDS, and TG/DSC. The results showed that the microspheres had uniform heterogeneous phases with amorphous Ni(OH)2 and CQDs. The sensor based on amorphous Ni(OH)2/CQDs microspheres showed remarkable electrocatalytic activity towards glucose oxidation comparing to the conventional crystalline Ni(OH)2, which included two linear range (20 μM-350 μM and 0.45mM-2.5 mM) with high selectivity of 2760.05 and 1853.64 μA mM-1cm-2. Moreover, the interference from the commonly interfering species such as urea, ascorbic acid, NaCl, L-proline and L-Valine, can be effectively avoided. The high sensitivity, wide glucose detection range and good selectivity of the electrode may be due to their synergistic effect of amorphous phase and CQDs incorporation. These findings may promote the application of amorphous Ni(OH)2 as advanced electrochemical glucose sensing materials.

Glassy phases and driven response of the phase-field-crystal model with random pinning.

PubMed

Granato, E; Ramos, J A P; Achim, C V; Lehikoinen, J; Ying, S C; Ala-Nissila, T; Elder, K R

2011-09-01

We study the structural correlations and the nonlinear response to a driving force of a two-dimensional phase-field-crystal model with random pinning. The model provides an effective continuous description of lattice systems in the presence of disordered external pinning centers, allowing for both elastic and plastic deformations. We find that the phase-field crystal with disorder assumes an amorphous glassy ground state, with only short-ranged positional and orientational correlations, even in the limit of weak disorder. Under increasing driving force, the pinned amorphous-glass phase evolves into a moving plastic-flow phase and then, finally, a moving smectic phase. The transverse response of the moving smectic phase shows a vanishing transverse critical force for increasing system sizes.

Effect of Secondary Phase Precipitation on the Corrosion Behavior of Duplex Stainless Steels

PubMed Central

Chan, Kai Wang; Tjong, Sie Chin

2014-01-01

Duplex stainless steels (DSSs) with austenitic and ferritic phases have been increasingly used for many industrial applications due to their good mechanical properties and corrosion resistance in acidic, caustic and marine environments. However, DSSs are susceptible to intergranular, pitting and stress corrosion in corrosive environments due to the formation of secondary phases. Such phases are induced in DSSs during the fabrication, improper heat treatment, welding process and prolonged exposure to high temperatures during their service lives. These include the precipitation of sigma and chi phases at 700–900 °C and spinodal decomposition of ferritic grains into Cr-rich and Cr-poor phases at 350–550 °C, respectively. This article gives the state-of the-art review on the microstructural evolution of secondary phase formation and their effects on the corrosion behavior of DSSs. PMID:28788129

Mechanically Induced Graphite-Nanodiamonds-Phase Transformations During High-Energy Ball Milling

NASA Astrophysics Data System (ADS)

El-Eskandarany, M. Sherif

2017-05-01

Due to their unusual mechanical, chemical, physical, optical, and biological properties, nearly spherical-like nanodiamonds have received much attention as desirable advanced nanomaterials for use in a wide spectrum of applications. Although, nanodiamonds can be successfully synthesized by several approaches, applications of high temperature and/or high pressure may restrict the real applications of such strategic nanomaterials. Distinct from the current preparation approaches used for nanodiamonds preparation, here we show a new process for preparing ultrafine nanodiamonds (3-5 nm) embedded in a homogeneous amorphous-carbon matrix. Our process started from high-energy ball milling of commercial graphite powders at ambient temperature under normal atmospheric helium gas pressure. The results have demonstrated graphite-single wall carbon nanotubes-amorphous-carbon-nanodiamonds phase transformations carried out through three subsequent stages of ball milling. Based on XRD and RAMAN analyses, the percentage of nanodiamond phase + C60 (crystalline phase) produced by ball milling was approximately 81%, while the amorphous phase amount was 19%. The pressure generated on the powder together the with temperature increase upon the ball-powder-ball collision is responsible for the phase transformations occurring in graphite powders.

Melt Extrusion of High-Dose Co-Amorphous Drug-Drug Combinations : Theme: Formulation and Manufacturing of Solid Dosage Forms Guest Editors: Tony Zhou and Tonglei Li.

PubMed

Arnfast, Lærke; Kamruzzaman, Md; Löbmann, Korbinian; Aho, Johanna; Baldursdottir, Stefania; Rades, Thomas; Rantanen, Jukka

2017-12-01

Many future drug products will be based on innovative manufacturing solutions, which will increase the need for a thorough understanding of the interplay between drug material properties and processability. In this study, hot melt extrusion of a drug-drug mixture with minimal amount of polymeric excipient was investigated. Using indomethacin-cimetidine as a model drug-drug system, processability of physical mixtures with and without 5% (w/w) of polyethylene oxide (PEO) were studied using Differential Scanning Calorimetry (DSC) and Small Amplitude Oscillatory Shear (SAOS) rheometry. Extrudates containing a co-amorphous glass solution were produced and the solid-state composition of these was studied with DSC. Rheological analysis indicated that the studied systems display viscosities higher than expected for small molecule melts and addition of PEO decreased the viscosity of the melt. Extrudates of indomethacin-cimetidine alone displayed amorphous-amorphous phase separation after 4 weeks of storage, whereas no phase separation was observed during the 16 week storage of the indomethacin-cimetidine extrudates containing 5% (w/w) PEO. Melt extrusion of co-amorphous extrudates with low amounts of polymer was found to be a feasible manufacturing technique. Addition of 5% (w/w) polymer reduced melt viscosity and prevented phase separation.

Rigid Amorphous Fraction in PLA Electrospun Fibers

NASA Astrophysics Data System (ADS)

Cebe, Peggy; Ma, Qian; Simona Cozza, Erika; Pyda, Marek; Mao, Bin; Zhu, Yazhe; Monticelli, Orietta

2013-03-01

Electrospun fibers of poly(lactic acid) (PLA) were formed by adopting a high-speed rotating wheel as the counter-electrode. The molecular orientation, crystallization mechanism, and phase structure and transitions of the aligned ES fibers were investigated. Using thermal analysis and wide angle X-ray scattering (WAXS), we evaluated the confinement that exists in as-spun amorphous, and heat-treated semicrystalline, fibers. Differential scanning calorimetry confirmed the existence of a constrained amorphous phase in as-spun aligned fibers, without the presence of crystals or fillers to serve as fixed physical constraints. Using WAXS, for the first time the mesophase fraction, consisting of oriented amorphous PLA chains, was quantitatively characterized in nanofibers. The authors acknowledge support from the National Science Foundation, Polymers Program under grant DMR-0602473. ESC acknowledges a Ph.D. grant supported by Italian Ministry of Education and Scientific Research.

Atomic transport during solid-phase epitaxial recrystallization of amorphous germanium

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

Radek, M.; Bracht, H., E-mail: bracht@uni-muenster.de; Johnson, B. C.

2015-08-24

The atomic mixing of matrix atoms during solid-phase epitaxy (SPE) is studied by means of isotopically enriched germanium (Ge) multilayer structures that were amorphized by Ge ion implantation up to a depth of 1.5 μm. Recrystallization of the amorphous structure is performed at temperatures between 350 °C and 450 °C. Secondary-ion-mass-spectrometry is used to determine the concentration-depth profiles of the Ge isotope before and after SPE. An upper limit of 0.5 nm is deduced for the displacement length of the Ge matrix atoms by the SPE process. This small displacement length is consistent with theoretical models and atomistic simulations of SPE, indicating that themore » SPE mechanism consists of bond-switching with nearest-neighbours across the amorphous-crystalline (a/c) interface.« less

Investigation of vapor-deposited amorphous ice and irradiated ice by molecular dynamics simulation.

PubMed

Guillot, Bertrand; Guissani, Yves

2004-03-01

With the purpose of clarifying a number of points raised in the experimental literature, we investigate by molecular dynamics simulation the thermodynamics, the structure and the vibrational properties of vapor-deposited amorphous ice (ASW) as well as the phase transformations experienced by crystalline and vitreous ice under ion bombardment. Concerning ASW, we have shown that by changing the conditions of the deposition process, it is possible to form either a nonmicroporous amorphous deposit whose density (approximately 1.0 g/cm3) is essentially invariant with the temperature of deposition, or a microporous sample whose density varies drastically upon temperature annealing. We find that ASW is energetically different from glassy water except at the glass transition temperature and above. Moreover, the molecular dynamics simulation shows no evidence for the formation of a high-density phase when depositing water molecules at very low temperature. In order to model the processing of interstellar ices by cosmic ray protons and heavy ions coming from the magnetospheric radiation environment around the giant planets, we bombarded samples of vitreous ice and cubic ice with 35 eV water molecules. After irradiation the recovered samples were found to be densified, the lower the temperature, the higher the density of the recovered sample. The analysis of the structure and vibrational properties of this new high-density phase of amorphous ice shows a close relationship with those of high-density amorphous ice obtained by pressure-induced amorphization. Copyright 2004 American Institute of Physics

Reduced platelet adhesion and improved corrosion resistance of superhydrophobic TiO₂-nanotube-coated 316L stainless steel.

PubMed

Huang, Qiaoling; Yang, Yun; Hu, Ronggang; Lin, Changjian; Sun, Lan; Vogler, Erwin A

2015-01-01

Superhydrophilic and superhydrophobic TiO2 nanotube (TNT) arrays were fabricated on 316L stainless steel (SS) to improve corrosion resistance and hemocompatibility of SS. Vertically-aligned superhydrophilic amorphous TNTs were fabricated on SS by electrochemical anodization of Ti films deposited on SS. Calcination was carried out to induce anatase phase (superhydrophilic), and fluorosilanization was used to convert superhydrophilicity to superhydrophobicity. The morphology, structure and surface wettability of the samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and contact angle goniometry. The effects of surface wettability on corrosion resistance and platelet adhesion were investigated. The results showed that crystalline phase (anatase vs. amorphous) and wettability strongly affected corrosion resistance and platelet adhesion. The superhydrophilic amorphous TNTs failed to protect SS from corrosion whereas superhydrophobic amorphous TNTs slightly improved corrosion resistance of SS. Both superhydrophilic and superhydrophobic anatase TNTs significantly improved corrosion resistance of SS. The superhydrophilic amorphous TNTs minimized platelet adhesion and activation whereas superhydrophilic anatase TNTs activated the formation of fibrin network. On the contrary, both superhydrophobic TNTs (superhydrophobic amorphous TNTs and superhydrophobic anatase TNTs) reduced platelet adhesion significantly and improved corrosion resistance regardless of crystalline phase. Superhydrophobic anatase TNTs coating on SS surface offers the opportunity for the application of SS as a promising permanent biomaterial in blood contacting biomedical devices, where both reducing platelets adhesion/activation and improving corrosion resistance can be effectively combined. Copyright © 2014 Elsevier B.V. All rights reserved.

Wear resistance of CuZr-based amorphous-forming alloys against bearing steel in 3.5% NaCl solution

NASA Astrophysics Data System (ADS)

Ji, Xiulin; Wang, Hui; Bao, Yayun; Zheng, Dingcong

2017-11-01

To investigate the amorphous-crystalline microstructure on the tribocorrosion of bulk metallic glasses (BMGs), 6 mm diameter rods of Cu46-xZr47Al7Agx (x = 0, 2, 4) amorphous-forming alloys with in situ crystalline and amorphous phases were fabricated by arc-melting and Cu-mould casting. Using a pin-on-disc tribometer, the tribo-pair composed by CuZr-based amorphous-forming alloys and AISI 52100 steel were studied in 3.5% NaCl solution. With the increase of Ag content from 0 to 4 at.%, the compressive fracture strength and the average hardness decrease firstly and then increase. Moreover, 4 at.% Ag addition increases the amount of amorphous phase obviously and inhibits the formation of brittle crystalline phase, resulting in the improvement of corrosion resistance and the corrosive wear resistance. The primary wear mechanism of the BMG composites is abrasive wear accompanying with corrosive wear. The tribocorrosion mass loss of Cu42Zr47Al7Ag4 composite is 1.5 mg after 816.8 m sliding distance at 0.75 m s-1 sliding velocity under 10 N load in NaCl solution. And the volume loss evaluated from the mass loss is about 20 times lower than that of AISI 304 SS. Thus, Cu42Zr47Al7Ag4 composite may be a good candidate in the tribology application under marine environment.

Stabilisation of Ce-Cu-Fe amorphous alloys by addition of Al

NASA Astrophysics Data System (ADS)

Kelhar, Luka; Ferčič, Jana; Boulet, Pascal; Maček-Kržmanc, Marjeta; Šturm, Sašo; Lamut, Martin; Markoli, Boštjan; Kobe, Spomenka; Dubois, Jean-Marie

2016-10-01

The present work describes the formation of amorphous alloys in the (Al1-xCex)62Cu25Fe13 quaternary system (0 ≤ x ≤ 1). When the amount of Ce falls in the range 0.67 ≤ x ≤ 0.83, the alloys obtained exhibit a completely amorphous structure confirmed by powder X-ray diffraction. Otherwise, at compositions x = 0.5, 0.58, 0.92 and 1, a primary crystalline phase forms together with an amorphous matrix. The crystallisation temperature (Tx) decreases with increasing Ce content, varying from 593 K for x = 0.5-383 K for x = 1. Composition x = 0.75 is considered as the best glass former, exhibiting a large supercooled liquid region of 40 K width that precedes crystallisation. In order to form bulk amorphous alloys, ribbons with this later composition were consolidated into few millimetre thick discs using pulsed electric current sintering at different temperatures, yet preserving the amorphous structure. Meanwhile, increasing temperature above 483 K triggers crystallisation of a primary phase isostructural to AlCe3. Further increase in the temperature up to 573 K yields a higher fraction of the crystalline phase. Testing mechanical properties, using nanoindentation, revealed that both elastic modulus (E) and hardness (H) depend on the Al content, ranging from E = 85.6 ± 3.7 GPa and H = 6.2 ± 0.7 GPa for x = 0.5 down to E = 39.8 ± 1.0 GPa and H = 3.1 ± 0.2 GPa for x = 0.92.

The role of Hydrogen and Creep in Intergranular Stress Corrosion Cracking of Alloy 600 and Alloy 690 in PWR Primary Water Environments ? a Review

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

Rebak, R B; Hua, F H

2004-07-12

Intergranular attack (IGA) and intergranular stress corrosion cracking (IGSCC) of Alloy 600 in PWR steam generator environment has been extensively studied for over 30 years without rendering a clear understanding of the essential mechanisms. The lack of understanding of the IGSCC mechanism is due to a complex interaction of numerous variables such as microstructure, thermomechanical processing, strain rate, water chemistry and electrochemical potential. Hydrogen plays an important role in all these variables. The complexity, however, significantly hinders a clearer and more fundamental understanding of the mechanism of hydrogen in enhancing intergranular cracking via whatever mechanism. In this work, an attemptmore » is made to review the role of hydrogen based on the current understanding of grain boundary structure and chemistry and intergranular fracture of nickel alloys, effect of hydrogen on electrochemical behavior of Alloy 600 and Alloy 690 (e.g. the passive film stability, polarization behavior and open-circuit potential) and effect of hydrogen on PWSCC behavior of Alloy 600 and Alloy 690. Mechanistic studies on the PWSCC are briefly reviewed. It is concluded that further studies on the role of hydrogen on intergranular cracking in both inert and primary side environments are needed. These studies should focus on the correlation of the results obtained at different laboratories by different methods on materials with different metallurgical and chemical parameters.« less

NDI method to locate intergranular corrosion around fastener holes in aluminum wing skins

NASA Astrophysics Data System (ADS)

Rutherford, Paul S.

1998-03-01

Contact between galvanically dissimilar metals, such as cadmium plated steel fasteners and aluminum wing skins are known to be a source of corrosion. There is a design requirement to fill the void between the contacting surfaces of steel fasteners with a wet sealant. However, if the contacting surface is damaged or a void exists between the fastener head and the aluminum skin, moisture can collect and intergranular corrosion may occur along aluminum grain boundaries, which run parallel to the surface of the wing skin. If intergranular corrosion is allowed to propagate, delamination of the thin layers of aluminum, known as exfoliation corrosion will occur. When this intergranular corrosion reaches an exfoliated state, extensive rework is involved in removing the corrosion. This paper discusses the results of a USAF E-3A Engineering Service Task 89-E3B3-16 to develop a nondestructive inspection procedure to detect intergranular corrosion in an incipient state before it reaches exfoliation. Eddy current and ultrasonic inspection techniques were evaluated. A novel ultrasonic pulse echo technique was developed which utilizes a focus transducer with a hand held fixture. Inspections were performed on test parts which were removed from the upper wing skin of a retired 707 which had varying degrees of intergranular and exfoliation corrosion. Inspection results are compared to the results from the mechanical rework of the wing skin and dissection of a wing skin fastener hole.

Depressurization amorphization of single-crystal boron carbide.

PubMed

Yan, X Q; Tang, Z; Zhang, L; Guo, J J; Jin, C Q; Zhang, Y; Goto, T; McCauley, J W; Chen, M W

2009-02-20

We report depressurization amorphization of single-crystal boron carbide (B4C) investigated by in situ high-pressure Raman spectroscopy. It was found that localized amorphization of B4C takes place during unloading from high pressures, and nonhydrostatic stresses play a critical role in the high-pressure phase transition. First-principles molecular dynamics simulations reveal that the depressurization amorphization results from pressure-induced irreversible bending of C-B-C atomic chains cross-linking 12 atom icosahedra at the rhombohedral vertices.

Three-dimensional studies of intergranular carbides in austenitic stainless steel.

PubMed

Ochi, Minoru; Kawano, Rika; Maeda, Takuya; Sato, Yukio; Teranishi, Ryo; Hara, Toru; Kikuchi, Masao; Kaneko, Kenji

2017-04-01

A large number of morphological studies of intergranular carbides in steels have always been carried out in two dimensions without considering their dispersion manners. In this article, focused ion beam serial-sectioning tomography was carried out to study the correlation among the grain boundary characteristics, the morphologies and the dispersions of intergranular carbides in 347 austenitic stainless steel. More than hundred intergranular carbides were characterized in three dimensions and finally classified into three different types, two types of carbides probably semi-coherent to one of the neighboring grains with plate-type morphology, and one type of carbides incoherent to both grains with rod-type morphology. In addition, the rod-type carbide was found as the largest number of carbides among three types. Since large numbers of defects, such as misfit dislocations, may be present at the grain boundaries, which can be ideal nucleation sites for intergranular rod-type carbide precipitation. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved.For permissions, please e-mail: journals.permissions@oup.com.

Double coating protection of Nd-Fe-B magnets: Intergranular phosphating treatment and copper plating

NASA Astrophysics Data System (ADS)

Zheng, Jingwu; Chen, Haibo; Qiao, Liang; Lin, Min; Jiang, Liqiang; Che, Shenglei; Hu, Yangwu

2014-12-01

In this work, a double coating protection technique of phosphating treatment and copper plating was made to improve the corrosion resistance of sintered Nd-Fe-B magnets. In other words, the intergranular region of sintered Nd-Fe-B is allowed to generate passive phosphate conversion coating through phosphating treatment, followed by the copper coating on the surface of sintered Nd-Fe-B. The morphology and corrosion resistance of the phosphated sintered Nd-Fe-B were observed using SEM and electrochemical method respectively. The phosphate conversion coating was formed more preferably on the intergranular region of sintered Nd-Fe-B than on the main crystal region; just after a short time of phosphating treatment, the intergranular region of sintered Nd-Fe-B has been covered by the phosphate conversion coating and the corrosion resistance is significantly improved. With the synergistic protection of the intergranular phosphorization and the followed copper electrodeposition, the corrosion resistance of the sintered Nd-Fe-B is significantly better than that with a single phosphate film or single plating protection.

Electrically conducting ternary amorphous fully oxidized materials and their application

NASA Technical Reports Server (NTRS)

Giauque, Pierre (Inventor); Nicolet, Marc (Inventor); Gasser, Stefan M. (Inventor); Kolawa, Elzbieta A. (Inventor); Cherry, Hillary (Inventor)

2004-01-01

Electrically active devices are formed using a special conducting material of the form Tm--Ox mixed with SiO2 where the materials are immiscible. The immiscible materials are forced together by using high energy process to form an amorphous phase of the two materials. The amorphous combination of the two materials is electrically conducting but forms an effective barrier.

Oxide formation and anodic polarization behavior of thin films of amorphous and crystalline FeCrP alloys prepared by ion beam mixing

NASA Astrophysics Data System (ADS)

Demaree, J. D.; Was, G. S.; Sorensen, N. R.

1991-07-01

An experimental program has been conducted to determine the effect of phosphorus on the corrosion and passivation behavior of FeCrP alloys. Chemically homogeneous 60 nm films of Fe10Cr xP ( x from 0 to 35 at.%) were prepared by multilayer evaporation followed by ion beam mixing with Kr + ions. Films with a phosphorus content of at least 25 at.% were found to be entirely amorphous, while films with 15 at.% P consisted of both amorphous and bcc phases. Recrystallization of the amorphous phase was accomplished by heating the samples to 450°C in a purified argon flow furnace. Electrochemical polarization tests in an acid solution have shown the Fe10Cr xP films to be more corrosion resistant than Fe10Cr, with the corrosion resistance increasing with the amount of P present. The corrosion resistance is not significantly affected when the amorphous films are recrystallized, indicating that the behavior is chemically controlled and not a result of the amorphous structure. When examined by XPS, the phosphorus appears to enhance passivation by encouraging Cr enrichment in the oxide and by incorporating in the oxide as phosphate.

Micromagnetic Study of Perpendicular Magnetic Recording Media

NASA Astrophysics Data System (ADS)

Dong, Yan

With increasing areal density in magnetic recording systems, perpendicular recording has successfully replaced longitudinal recording to mitigate the superparamagnetic limit. The extensive theoretical and experimental research associated with perpendicular magnetic recording media has contributed significantly to improving magnetic recording performance. Micromagnetic studies on perpendicular recording media, including aspects of the design of hybrid soft underlayers, media noise properties, inter-grain exchange characterization and ultra-high density bit patterned media recording, are presented in this dissertation. To improve the writability of recording media, one needs to reduce the head-to-keeper spacing while maintaining a good texture growth for the recording layer. A hybrid soft underlayer, consisting of a thin crystalline soft underlayer stacked above a non-magnetic seed layer and a conventional amorphous soft underlayer, provides an alternative approach for reducing the effective head-to-keeper spacing in perpendicular recording. Micromagnetic simulations indicate that the media using a hybrid soft underlayer helps enhance the effective field and the field gradient in comparison with conventional media that uses only an amorphous soft underlayer. The hybrid soft underlayer can support a thicker non-magnetic seed layer yet achieve an equivalent or better effective field and field gradient. A noise plateau for intermediate recording densities is observed for a recording layer of typical magnetization. Medium noise characteristics and transition jitter in perpendicular magnetic recording are explored using micromagnetic simulation. The plateau is replaced by a normal linear dependence of noise on recording density for a low magnetization recording layer. We show analytically that a source of the plateau is similar to that producing the Non-Linear-Transition-Shift of signal. In particular, magnetostatic effects are predicted to produce positive correlation of jitter and thus negative correlation of noise at the densities associated with the plateau. One focus for developing perpendicular recording media is on how to extract intergranular exchange coupling and intrinsic anisotropy field dispersion. A micromagnetic numerical technique is developed to effectively separate the effects of intergranular exchange coupling and anisotropy dispersion by finding their correlation to differentiated M-H curves with different initial magnetization states, even in the presence of thermal fluctuation. The validity of this method is investigated with a series of intergranular exchange couplings and anisotropy dispersions for different media thickness. This characterization method allows for an experimental measurement employing a vibrating sample magnetometer (VSM). Bit patterned media have been suggested to extend areal density beyond 1 Tbit/in2. The feasibility of 4 Tbit/in2 bit patterned recording is determined by aspects of write head design and media fabrication, and is estimated by the bit error rate. Micromagnetic specifications including 2.3:1 BAR bit patterned exchange coupled composite media, trailing shield, and side shields are proposed to meet the requirement of 3x10 -4 bit error rate, 4 nm fly height, 5% switching field distribution, 5% timing and 5% jitter errors for 4 Tbit/in2 bit-patterned recording. Demagnetizing field distribution is examined by studying the shielding effect of the side shields on the stray field from the neighboring dots. For recording self-assembled bit-patterned media, the head design writes two staggered tracks in a single pass and has maximum perpendicular field gradients of 580 Oe/nm along the down-track direction and 476 Oe/nm along the cross-track direction. The geometry demanded by self-assembly reduces recording density to 2.9 Tbit/in 2.

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE PAGES

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin; ...

2018-04-26

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

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

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars.

PubMed

Sklute, Elizabeth C; Rogers, A Deanne; Gregerson, Jason C; Jensen, Heidi B; Reeder, Richard J; Dyar, M Darby

2018-03-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multi-component (Fe 2 (SO 4 ) 3 ± Ca, Na, Mg, Fe, Cl, HCO 3 ) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials.

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars

NASA Astrophysics Data System (ADS)

Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby

2018-03-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multicomponent (Fe2(SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21 °C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials.

Amorphous salts formed from rapid dehydration of multicomponent chloride and ferric sulfate brines: Implications for Mars

PubMed Central

Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby

2018-01-01

Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca–, Na–, Mg– and Fe–chloride brines and multi-component (Fe2 (SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe–chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials. PMID:29670302

Influence of the cooling rate and the blend ratio on the physical stability of co-amorphous naproxen/indomethacin.

PubMed

Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S

2016-12-01

Co-amorphization represents a promising approach to increase the physical stability and dissolution rate of amorphous active pharmaceutical ingredients (APIs) as an alternative to polymer glass solutions. For amorphous and co-amorphous systems, it is reported that the preparation method and the blend ratio play major roles with regard to the resulting physical stability. Therefore, in the present study, co-amorphous naproxen-indomethacin (NAP/IND) was prepared by melt-quenching at three different cooling rates and at ten different NAP/IND blend ratios. The samples were analyzed using XRPD and FTIR, both directly after preparation and during storage to investigate their physical stabilities. All cooling methods led to fully amorphous samples, but with significantly different physical stabilities. Samples prepared by fast cooling had a higher degree of crystallinity after 300d of storage than samples prepared by intermediate cooling and slow cooling. Intermediate cooling was subsequently used to prepare co-amorphous NAP/IND at different blend ratios. In a previous study, it was postulated that the equimolar (0.5:0.5) co-amorphous blend of NAP/IND is most stable. However, in the present study the physically most stable blend was found for a NAP/IND ratio of 0.6:0.4, which also represents the eutectic composition of the crystalline NAP/γ-IND system. This indicates that the eutectic point may be of major importance for the stability of binary co-amorphous systems. Slight deviations from the optimal naproxen molar fraction led to significant recrystallization during storage. Either naproxen or γ-indomethacin recrystallized until a naproxen molar fraction of about 0.6 in the residual co-amorphous phase was reached again. In conclusion, the physical stability of co-amorphous NAP/IND may be significantly improved, if suitable preparation conditions and the optimal phase composition are chosen. Copyright © 2016 Elsevier B.V. All rights reserved.

Amorphization of Ta2O5 under swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Cusick, Alex B.; Lang, Maik; Zhang, Fuxiang; Sun, Kai; Li, Weixing; Kluth, Patrick; Trautmann, Christina; Ewing, Rodney C.

2017-09-01

Crystalline Ta2O5 powder is shown to amorphize under 2.2 GeV 197Au ion irradiation. Synchrotron X-ray diffraction (XRD), Raman spectroscopy, small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM) were used to characterize the structural transition from crystalline to fully-amorphous. Based on Rietveld refinement of XRD data, the initial structure is orthorhombic (P2mm) with a very large unit cell (a = 6.20, b = 40.29, c = 3.89 Å; V = 971.7 Å3), ideally containing 22 Ta and 55 O atoms. At a fluence of approximately 3 × 1011 ions/cm2, a diffuse amorphous background becomes evident, increasing in intensity relative to diffraction maxima until full amorphization is achieved at approximately 3 × 1012 ions/cm2. An anisotropic distortion of the orthorhombic structure occurred during the amorphization process, with an approximately constant unit cell volume. The amorphous phase fraction as a function of fluence was determined, yielding a trend that is consistent with a direct-impact model for amorphization. SAXS and TEM data indicate that ion tracks exhibit a core-shell morphology. Raman data show that the amorphous phase is comprised of TaO6 and TaO5 coordination-polyhedra in contrast to the TaO6 and TaO7 units that exist in crystalline Ta2O5. Analysis of Raman data shows that oxygen-deficiency increases with fluence, indicating a loss of oxygen that leads to an estimated final stoichiometry of Ta2O4.2 at a fluence of 1 × 1013 ions/cm2.

Gas uptake and chemical aging of semisolid organic aerosol particles

PubMed Central

Shiraiwa, Manabu; Ammann, Markus; Koop, Thomas; Pöschl, Ulrich

2011-01-01

Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate. PMID:21690350

Microstructural modifications induced by accelerated aging and lipid absorption in remelted and annealed UHMWPEs for total hip arthroplasty

PubMed Central

Puppulin, Leonardo; Zhu, Wenliang; Sugano, Nobuhiko

2014-01-01

Three types of commercially available ultra-high molecular weight polyethylene (UHMWPE) acetabular cups currently used in total hip arthroplasty have been studied by means of Raman micro-spectroscopy to unfold the microstructural modification induced by the oxidative degradation after accelerated aging with and without lipid absorption. The three investigated materials were produced by three different manufacturing procedures, as follows: irradiation followed by remelting, one-step irradiation followed by annealing, 3-step irradiation and annealing. Clear microstructural differences were observed in terms of phase contents (i.e. amorphous, crystalline and intermediate phase fraction). The three-step annealed material showed the highest crystallinity fraction in the bulk, while the remelted polyethylene is clearly characterized by the lowest content of crystalline phase and the highest content of amorphous phase. After accelerated aging either with or without lipids, the amount of amorphous phase decreased in all the samples as a consequence of the oxidation-induced recrystallization. The most remarkable variations of phase contents were detected in the remelted and in the single-step annealed materials. The presence of lipids triggered oxidative degradation especially in the remelted polyethylene. Such experimental evidence might be explained by the highest amount of amorphous phase in which lipids can be absorbed prior to accelerated aging. The results of these spectroscopic characterizations help to rationalize the complex effect of different irradiation and post-irradiation treatments on the UHMWPE microstructure and gives useful information on how significantly any single step of the manufacturing procedures might affect the oxidative degradation of the polymer. PMID:25179830

Neutron irradiation and high temperature effects on amorphous Fe-based nano-coatings on steel - A macroscopic assessment

NASA Astrophysics Data System (ADS)

Simos, N.; Zhong, Z.; Dooryhee, E.; Ghose, S.; Gill, S.; Camino, F.; Şavklıyıldız, İ.; Akdoğan, E. K.

2017-06-01

The study revealed that loss of ductility in an amorphous Fe-alloy coating on a steel substrate composite structure was essentially prevented from occurring, following radiation with modest neutron doses of ∼2 × 1018 n/cm2. At the higher neutron dose of ∼2 × 1019, macroscopic stress-strain analysis showed that the amorphous Fe-alloy nanostructured coating, while still amorphous, experienced radiation-induced embrittlement, no longer offering protection against ductility loss in the coating-substrate composite structure. Neutron irradiation in a corrosive environment revealed exemplary oxidation/corrosion resistance of the amorphous Fe-alloy coating, which is attributed to the formation of the Fe2B phase in the coating. To establish the impact of elevated temperatures on the amorphous-to-crystalline transition in the amorphous Fe-alloy, electron microscopy was carried out which confirmed the radiation-induced suppression of crystallization in the amorphous Fe-alloy nanostructured coating.

On the Preservation of Intergranular Coesite in UHP Eclogite at Yangkou Bay, Sulu belt of eastern China

NASA Astrophysics Data System (ADS)

Wang, L.; Wang, S.; Brown, M.

2016-12-01

In contrast to coesite that occurs as inclusions in zircon and rock-forming minerals, intergranular coesite is preserved in UHP eclogite at Yangkou in the Sulu belt. The survival of intergranular coesite is intriguing because the eclogite experienced phengite growth and partial melting during exhumation. The coesite eclogite occurs as rootless isoclinal fold noses within quartz-rich schist which contains 10-20 vol% phengite, whereas phengite is absent from coesite eclogite in the fold noses. To evaluate the factors that control preservation of intergranular coesite, four samples representative of different stages along the retrograde P-T path were selected for study. For each sample we determined the number of intergranular coesite grains per cm2 and the OH content of garnet and omphacite. As the number of coesite grains decreases, the bulk rock OH content increases from <200 ppm in phengite-free coesite eclogite to 200-260 ppm in phengite-bearing (<5 vol%) coesite eclogite and up to a maximum of 430-438 ppm in quartz eclogite ( 10 vol% phengite). However, the OH content drops to a minimum of 59 ppm in residual eclogite resulting from melt drainage. This trend implies that the volume of fluid increased sufficiently during exhumation to facilitate the growth of phengite and the transformation to quartz of intergranular coesite outside of the fold noses. The fluid is inferred to have been a supercritical fluid probably residual from prograde dehydration but also derived by dissolution of nominally anhydrous minerals. Post-metamorphic-peak deformation combined with fluid percolation along sheared fold limbs induced phengite growth during initial exhumation and then facilitated partial melting. In contrast, fold hinges in competent layers are unfavourable sites for fluid penetration. At Yangkou, the intergranular coesite is preserved in the fold noses where it was protected from both penetrative deformation and fluid ingress. Therefore, the fold noses maintained a relatively dry environment that allowed preservation of the intergranular coesite. Thus, deformation partitioning and strain localization impose local controls on fluid distribution and migration in UHP eclogite. This study informs our understanding of variations in fluid regime during exhumation of deeply subducted continental crust.

Structure-property relationships in semicrystalline copolymers and ionomers

NASA Astrophysics Data System (ADS)

Wakabayashi, Katsuyuki

Many outstanding physical properties of ethylene/(meth)acrylic acid (E/(M)AA) copolymers and ionomers are associated with their nanometer-scale morphology, which consists of ethylene crystallites, amorphous segments, and acid/ionic functional groups. The goal of this dissertation is a fundamental understanding of the interplay between these structural motifs and the consequent effects on the material properties. We identify small-strain modulus as a key mechanical property and investigate its dependence upon material structure through X-ray scattering, calorimetry, and mechanical property measurements. We first treat E/(M)AA copolymers as composites of polyethylene crystallites and amorphous regions, and establish a quantitative combining rule to describe the copolymer modulus. At temperatures above the Tg of the copolymers, a monotonic increase in modulus with crystallinity is quantitatively described by the Davies equation for two-phase composites, which serves as the basis for separating the effects of amorphous and crystalline phases throughout this dissertation. The room-temperature modulus of E/(M)AA copolymers is concurrently affected by ethylene crystallinity and proximity to the amorphous phase Tg, which rises through room temperature with increasing comonomer content. In E/(M)AA ionomers, phase separation and aggregation of ionic groups provide additional stiffness and toughness. Ionomers are modeled as composites of crystallites and ionically crosslinked rubber, whose amorphous phase modulus far above the ionomer Tg is satisfactorily described by simple rubber elasticity theory. Thermomechanical analyses probe the multi-step relaxation behavior of E/(M)AA ionomers and lead to the development of a new semicrystalline ionomer morphological model, wherein secondary crystallites and ionic aggregates together form rigid percolated pathways throughout the amorphous phase. Metal soaps are oligomeric analogs of E/(M)AA ionomers, which can be blended into ionomers to achieve high ion content and in turn desirable physical properties. We assess the compatibility of various types of metal soaps with E/(M)AA ionomers, and investigate how the soap modifies the ionomers' structure and properties. The mechanical properties and phase behavior of these hybrids, which are found to differ significantly depending on the neutralizing cation type and crystallinizability of the metal soap, are traced back to various levels of molecular coassembly involving the hydrocarbon chains and/or the ionic groups of both entities.

Creation and formation mechanism of new carbon phases constructed by amorphous carbon

NASA Astrophysics Data System (ADS)

Yao, Mingguang; Cui, Wen; Liu, Bingbing

Our recent effort is focusing on the creation of new hard/superhard carbon phases constructed by disordered carbons or amorphous carbon clusters under high pressure. We showed that the pressure-induced amorphous hard carbon clusters from collapsed fullerenes can be used as building blocks (BBs) for constructing novel carbon structures. This new strategy has been verified by compressing a series of intercalated fullerides, pre-designed by selecting various dopants with special features. We demonstrate that the boundaries of the amorphous BBs are mediated by intercalated dopants and several new superhard materials have been prepared. We also found that the dopant-mediated BBs can be arranged in either ordered or disordered structures, both of which can be hard enough to indent the diamond anvils. The hardening mechanisms of the new phases have also been discussed. For the glassy carbon (GC) constructructed by disordered fullerene-like nanosized fragments, we also found that these disordered fragments can bond and the compressed GC transformed into a transparent superhard phase. Such pressure-induced transformation has been discovered to be driven by a novel mechanism (unpublished). By understanding the mechanisms we can clarify the controversial results on glassy carbon reported recently. The authors would like to thank the financial support from the National Natural Science Foundation of China (No. 11474121, 51320105007).

Phase transitions in biogenic amorphous calcium carbonate

NASA Astrophysics Data System (ADS)

Gong, Yutao

Geological calcium carbonate exists in both crystalline phases and amorphous phases. Compared with crystalline calcium carbonate, such as calcite, aragonite and vaterite, the amorphous calcium carbonate (ACC) is unstable. Unlike geological calcium carbonate crystals, crystalline sea urchin spicules (99.9 wt % calcium carbonate and 0.1 wt % proteins) do not present facets. To explain this property, crystal formation via amorphous precursors was proposed in theory. And previous research reported experimental evidence of ACC on the surface of forming sea urchin spicules. By using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), we studied cross-sections of fresh sea urchin spicules at different stages (36h, 48h and 72h after fertilization) and observed the transition sequence of three mineral phases: hydrated ACC → dehydrated ACC → biogenic calcite. In addition, we unexpectedly found hydrated ACC nanoparticles that are surrounded by biogenic calcite. This observation indicates the dehydration from hydrated ACC to dehydrated ACC is inhibited, resulting in stabilization of hydrated ACC nanoparticles. We thought that the dehydration was inhibited by protein matrix components occluded within the biomineral, and we designed an in vitro assay to test the hypothesis. By utilizing XANES-PEEM, we found that SM50, the most abundant occluded matrix protein in sea urchin spicules, has the function to stabilize hydrated ACC in vitro.

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

Near-infrared–driven decomposition of metal precursors yields amorphous electrocatalytic films

PubMed Central

Salvatore, Danielle A.; Dettelbach, Kevan E.; Hudkins, Jesse R.; Berlinguette, Curtis P.

2015-01-01

Amorphous metal-based films lacking long-range atomic order have found utility in applications ranging from electronics applications to heterogeneous catalysis. Notwithstanding, there is a limited set of fabrication methods available for making amorphous films, particularly in the absence of a conducting substrate. We introduce herein a scalable preparative method for accessing oxidized and reduced phases of amorphous films that involves the efficient decomposition of molecular precursors, including simple metal salts, by exposure to near-infrared (NIR) radiation. The NIR-driven decomposition process provides sufficient localized heating to trigger the liberation of the ligand from solution-deposited precursors on substrates, but insufficient thermal energy to form crystalline phases. This method provides access to state-of-the-art electrocatalyst films, as demonstrated herein for the electrolysis of water, and extends the scope of usable substrates to include nonconducting and temperature-sensitive platforms. PMID:26601148

On the effect of Ti on the stability of amorphous indium zinc oxide used in thin film transistor applications

NASA Astrophysics Data System (ADS)

Lee, Sunghwan; Paine, David C.

2011-06-01

In2O3-based amorphous oxide channel materials are of increasing interest for thin film transisitor applications due, in part, to the remarkable stability of this class of materials amorphous structure and electronic properties. We report that this stability is degraded in the presence of Ti, which is widely used as a contact and/or adhesion layer. A cross-sectional transmission electron microscopy analysis, supported by glancing incident angle x-ray and selected area diffraction examination, shows that amorphous indium zinc oxide in contact with Ti undergoes crystallization to the bixbyite phase and reacts to form the rutile phase of TiO2 at a temperature of 200 °C. A basic thermodynamic analysis is presented and forms the basis of a model that describes both the crystallization and the resistivity decrease.

Crystallization Behavior of A Bulk Amorphous Mg62Cu26Y12 Alloy

NASA Astrophysics Data System (ADS)

Wu, Shyue-Sheng; Chin, Tsung-Shune; Su, Kuo-Chang

1994-07-01

The crystallization temperature, the associated activation energy and the crystallized structure of a bulk amorphous Mg62Cu26Y12 alloy with a diameter of 2.5 mm were studied. It possesses a one-step crystallization behavior. The crystallization reaction was found to be represented by: AM(MG62Cu26Y12)→Mg2Cu+MgY+CuY+Mg, ( Tx=188°C, Eac=134 kJ/mol) where AM represents the amorphous state, T x the crystallization temperature at an infinitesimal heating rate, and E ac the associated activation energy. The amount of crystalline phases were found to be Mg2Cu:MgY:CuY=76:17:7. The Mg phase is identifiable only by high resolution electron microscopy, not by X-ray diffraction. The crystallization leads to a sharp rise in electrical resistivity which is reversed to those of iron-based amorphous alloys.

NMR studies of electronic structure in crystalline and amorphous Zr2PdH/x/

NASA Technical Reports Server (NTRS)

Bowman, R. C., Jr.; Johnson, W. L.; Maeland, A. J.; Rhim, W.-K.

1983-01-01

The proton Knight shifts and spin-lattice relaxation times have been measured in crystalline and amorphous Ze2PdH(x). Core polarization from the Zr d-band dominates the proton hyperfine interactions. The density of Fermi level d-electron states is reduced in the amorphous phase relative to the electron density in crystalline Zr2PdH(x).

Reversible switching between pressure-induced amorphization and thermal-driven recrystallization in VO2(B) nanosheets

DOE PAGES

Wang, Yonggang; Zhu, Jinlong; Yang, Wenge; ...

2016-07-18

Pressure-induced amorphization (PIA) and thermal-driven recrystallization have been observed in many crystalline materials. However, controllable switching between PIA and a metastable phase has not been described yet, due to the challenge to establish feasible switching methods to control the pressure and temperature precisely. Here, we demonstrate a reversible switching between PIA and thermally-driven recrystallization of VO 2(B) nanosheets. Comprehensive in situ experiments are performed to establish the precise conditions of the reversible phase transformations, which are normally hindered but occur with stimuli beyond the energy barrier. Spectral evidence and theoretical calculations reveal the pressure–structure relationship and the role of flexiblemore » VO x polyhedra in the structural switching process. Anomalous resistivity evolution and the participation of spin in the reversible phase transition are observed for the first time. Our findings have significant implications for the design of phase switching devices and the exploration of hidden amorphous materials.« less

Revealing the Origins of Mechanically Induced Fluorescence Changes in Organic Molecular Crystals.

PubMed

Wilbraham, Liam; Louis, Marine; Alberga, Domenico; Brosseau, Arnaud; Guillot, Régis; Ito, Fuyuki; Labat, Frédéric; Métivier, Rémi; Allain, Clémence; Ciofini, Ilaria

2018-05-29

Mechanofluorochromic molecular materials display a change in fluorescence color through mechanical stress. Complex structure-property relationships in both the crystalline and amorphous phases of these materials govern both the presence and strength of this behavior, which is usually deemed the result of a mechanically induced phase transition. However, the precise nature of the emitting species in each phase is often a matter of speculation, resulting from experimental data that are difficult to interpret, and a lack of an acceptable theoretical model capable of capturing complex environmental effects. With a combined strategy using sophisticated experimental techniques and a new theoretical approach, here the varied mechanofluorochromic behavior of a series of difluoroboron diketonates is shown to be driven by the formation of low-energy exciton traps in the amorphous phase, with a limited number of traps giving rise to the full change in fluorescence color. The results highlight intrinsic structural links between crystalline and amorphous phases, and how these may be exploited for further development of powerful mechanofluorochromic assemblies, in line with modern crystal engineering approaches. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relation between bandgap and resistance drift in amorphous phase change materials

PubMed Central

Rütten, Martin; Kaes, Matthias; Albert, Andreas; Wuttig, Matthias; Salinga, Martin

2015-01-01

Memory based on phase change materials is currently the most promising candidate for bridging the gap in access time between memory and storage in traditional memory hierarchy. However, multilevel storage is still hindered by the so-called resistance drift commonly related to structural relaxation of the amorphous phase. Here, we present the temporal evolution of infrared spectra measured on amorphous thin films of the three phase change materials Ag4In3Sb67Te26, GeTe and the most popular Ge2Sb2Te5. A widening of the bandgap upon annealing accompanied by a decrease of the optical dielectric constant ε∞ is observed for all three materials. Quantitative comparison with experimental data for the apparent activation energy of conduction reveals that the temporal evolution of bandgap and activation energy can be decoupled. The case of Ag4In3Sb67Te26, where the increase of activation energy is significantly smaller than the bandgap widening, demonstrates the possibility to identify new phase change materials with reduced resistance drift. PMID:26621533

Relation between bandgap and resistance drift in amorphous phase change materials.

PubMed

Rütten, Martin; Kaes, Matthias; Albert, Andreas; Wuttig, Matthias; Salinga, Martin

2015-12-01

Memory based on phase change materials is currently the most promising candidate for bridging the gap in access time between memory and storage in traditional memory hierarchy. However, multilevel storage is still hindered by the so-called resistance drift commonly related to structural relaxation of the amorphous phase. Here, we present the temporal evolution of infrared spectra measured on amorphous thin films of the three phase change materials Ag4In3Sb67Te26, GeTe and the most popular Ge2Sb2Te5. A widening of the bandgap upon annealing accompanied by a decrease of the optical dielectric constant ε∞ is observed for all three materials. Quantitative comparison with experimental data for the apparent activation energy of conduction reveals that the temporal evolution of bandgap and activation energy can be decoupled. The case of Ag4In3Sb67Te26, where the increase of activation energy is significantly smaller than the bandgap widening, demonstrates the possibility to identify new phase change materials with reduced resistance drift.

Chimeric Plastics : a new class of thermoplastic

NASA Astrophysics Data System (ADS)

Sonnenschein, Mark

A new class of thermoplastics (dubbed ``Chimerics'') is described that exhibits a high temperature glass transition followed by high performance elastomer properties, prior to melting. These transparent materials are comprised of co-continuous phase-separated block copolymers. One block is an amorphous glass with a high glass transition temperature, and the second is a higher temperature phase transition block creating virtual thermoreversible crosslinks. The material properties are highly influenced by phase separation on the order of 10-30 nanometers. At lower temperatures the polymer reflects the sum of the block copolymer properties. As the amorphous phase glass transition is exceeded, the virtual crosslinks of the higher temperature second phase dominate the plastic properties, resulting in rubber-like elasticity.

High strength nanostructured Al-based alloys through optimized processing of rapidly quenched amorphous precursors.

PubMed

Kim, Song-Yi; Lee, Gwang-Yeob; Park, Gyu-Hyeon; Kim, Hyeon-Ah; Lee, A-Young; Scudino, Sergio; Prashanth, Konda Gokuldoss; Kim, Do-Hyang; Eckert, Jürgen; Lee, Min-Ha

2018-01-18

We report the methods increasing both strength and ductility of aluminum alloys transformed from amorphous precursor. The mechanical properties of bulk samples produced by spark-plasma sintering (SPS) of amorphous Al-Ni-Co-Dy powders at temperatures above 673 K are significantly enhanced by in-situ crystallization of nano-scale intermetallic compounds during the SPS process. The spark plasma sintered Al 84 Ni 7 Co 3 Dy 6 bulk specimens exhibit 1433 MPa compressive yield strength and 1773 MPa maximum strength together with 5.6% plastic strain, respectively. The addition of Dy enhances the thermal stability of primary fcc Al in the amorphous Al-TM -RE alloy. The precipitation of intermetallic phases by crystallization of the remaining amorphous matrix plays important role to restrict the growth of the fcc Al phase and contributes to the improvement of the mechanical properties. Such fully crystalline nano- or ultrafine-scale Al-Ni-Co-Dy systems are considered promising for industrial application because their superior mechanical properties in terms of a combination of very high room temperature strength combined with good ductility.

Anisotropic expansion and amorphization of Ga2O3 irradiated with 946 MeV Au ions

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Lang, Maik; Severin, Daniel; Bender, Markus; Trautmann, Christina; Ewing, Rodney C.

2016-05-01

The structural response of β-Ga2O3 to irradiation-induced electronic excitation was investigated. A polycrystalline pellet of this material was irradiated with 946 MeV Au ions and the resulting structural modifications were characterized using in situ X-ray diffraction analysis at various ion fluences, up to 1 × 1013 cm-2. Amorphization was induced, with the accumulation of the amorphous phase following a single-impact mechanism in which each ion produces an amorphous ion track along its path. Concurrent with this phase transformation, an increase in the unit cell volume of the material was observed and quantified using Rietveld refinement. This unit cell expansion increased as a function of ion fluence before saturating at 1.8%. This effect is attributed to the generation of defects in an ion track shell region surrounding the amorphous track cores. The unit cell parameter increase was highly anisotropic, with no observed expansion in the [0 1 0] direction. This may be due to the structure of β-Ga2O3, which exhibits empty channels of connected interstitial sites oriented in this direction.

An electron tunneling study of superconductivity in amorphous Sn(sub 1-x)Cu(sub x) thin films

NASA Technical Reports Server (NTRS)

Naugle, D. G.; Watson, P. W., III; Rathnayaka, K. D. D.

1995-01-01

The amorphous phase of Sn would have a superconducting transition temperature near 8 K, much higher than that of crystalline Sn with T(sub c) = 3.5 K. To obtain the amorphous phase, however, it is necessary to use a Sn alloy, usually Cu, and quench condense the alloy films onto a liquid He temperature substrate. Alloying with Cu reduces the superconducting transition temperature almost linearly with Cu concentration with an extrapolation of T(sub c) to zero for x = 0.85. Analysis of the tunneling characteristics between a normal metal electrode with an insulating barrier and superconducting amorphous Sn-Cu films provides detailed information on the changes in the electron-phonon coupling which determines T(sub c) in these alloys. The change from very strong electron-phonon coupling to weak-coupling with the increase in Cu content of amorphous Sn-Cu alloys for the range 0.08 is less than or equal to x is less than or equal to 0.41 is presented and discussed in terms of theories of electron-phonon coupling in disordered metals.

The mineral phase in the cuticles of two species of Crustacea consists of magnesium calcite, amorphous calcium carbonate, and amorphous calcium phosphate.

PubMed

Becker, Alexander; Ziegler, Andreas; Epple, Matthias

2005-05-21

The cuticules (shells) of the woodlice Porcellio scaber and Armadillidium vulgare were analysed with respect to their content of inorganic material. It was found that the cuticles consist of crystalline magnesium calcite, amorphous calcium carbonate (ACC), and amorphous calcium phosphate (ACP), besides small amounts of water and an organic matrix. It is concluded that the cuticle, which constitutes a mineralized protective organ, is chemically adapted to the biological requirements by this combination of different materials.

Amorphous Zn₂GeO₄ Nanoparticles as Anodes with High Reversible Capacity and Long Cycling Life for Li-ion Batteries

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

Yi, Ran; Feng, Jinkui; Lv, Dongping

2013-07-30

Amorphous and crystalline Zn₂GeO₄ nanoparticles were prepared and characterized as anode materials for Li-ion batteries. A higher reversible specific capacity of 1250 mAh/g after 500 cycles and excellent rate capability were obtained for amorphous Zn₂GeO₄ nanoparticles, compared to that of crystalline Zn₂GeO₄ nanoparticles. Small particle size, amorphous phase and incorporation of zinc and oxygen contribute synergetically to the improved performance by effectively mitigating the huge volume variations during lithiation and delithiation process.

Microstructures evolution and physical properties of laser induced NbC modified nanocrystalline composites

NASA Astrophysics Data System (ADS)

Li, Jianing; Liu, Kegao; Yuan, Xingdong; Shan, Feihu; Zhang, Bolun; Wang, Zhe; Xu, Wenzhuo; Zhang, Zheng; An, Xiangchen

2017-10-01

The nanoscale quasicrystals (NQs), amorphous and ultrafine nanocrystals (UNs) modified hard composites are produced by laser cladding (LC) of the Ni60A-TiC-NbC-Sb mixed powders on the additive manufacturing (AM) TA1 titanium alloy. The LC technique is favorable to formations of icosahedral quasicrystals (I-phase) with five-fold symmetry due to its rapid cooling and solidification characteristics. The formation mechanism of this I-phase is explained here. Under the actions of NQs, amorphous and UNs, such LC composites exhibited an extremely high micro-hardness. UNs may also intertwin with amorphous, forming yarn-shape materials. This research provides essential theoretical basis to improve the quality of laser-treated composites.

Pressure-induced amorphization and collapse of magnetic order in the type-I clathrate Eu8Ga16Ge30

NASA Astrophysics Data System (ADS)

Mardegan, J. R. L.; Fabbris, G.; Veiga, L. S. I.; Adriano, C.; Avila, M. A.; Haskel, D.; Giles, C.

2013-10-01

We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume collapse is observed prior to the crystalline-amorphous phase transition which takes place when the unit cell volume is reduced to 81% of its ambient pressure value. Fits of the pressure-dependent relative volume to a Murnaghan equation of state yield a bulk modulus B0=65±3 GPa and a pressure derivative B0'=3.3±0.5. The Eu L2-edge XMCD data shows quenching of the magnetic order at a pressure coincident with the crystalline-amorphous phase transition. This information along with the persistence of an Eu2+ valence state observed in the XANES spectra up to the highest pressure point (22 GPa) indicates that the suppression of XMCD intensity is due to the loss of long range magnetic order. When compared with other clathrates, the results point to the importance of guest ion-cage interactions in determining the mechanical stability of the framework structure and the critical pressure for amorphization. Finally, the crystalline structure is not found to recover after pressure release, resulting in an amorphous material that is at least metastable at ambient pressure and temperature.

Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

PubMed

Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

2017-12-13

In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

Analysis of intergranular fission-gas bubble-size distributions in irradiated uranium-molybdenum alloy fuel

NASA Astrophysics Data System (ADS)

Rest, J.; Hofman, G. L.; Kim, Yeon Soo

2009-04-01

An analytical model for the nucleation and growth of intra and intergranular fission-gas bubbles is used to characterize fission-gas bubble development in low-enriched U-Mo alloy fuel irradiated in the advanced test reactor in Idaho as part of the Reduced Enrichment for Research and Test Reactor (RERTR) program. Fuel burnup was limited to less than ˜7.8 at.% U in order to capture the fuel-swelling stage prior to irradiation-induced recrystallization. The model couples the calculation of the time evolution of the average intergranular bubble radius and number density to the calculation of the intergranular bubble-size distribution based on differential growth rate and sputtering coalescence processes. Recent results on TEM analysis of intragranular bubbles in U-Mo were used to set the irradiation-induced diffusivity and re-solution rate in the bubble-swelling model. Using these values, good agreement was obtained for intergranular bubble distribution compared against measured post-irradiation examination (PIE) data using grain-boundary diffusion enhancement factors of 15-125, depending on the Mo concentration. This range of enhancement factors is consistent with values obtained in the literature.

Three-dimensional study of grain boundary engineering effects on intergranular stress corrosion cracking of 316 stainless steel in high temperature water

NASA Astrophysics Data System (ADS)

Liu, Tingguang; Xia, Shuang; Bai, Qin; Zhou, Bangxin; Zhang, Lefu; Lu, Yonghao; Shoji, Tetsuo

2018-01-01

The intergranular cracks and grain boundary (GB) network of a GB-engineered 316 stainless steel after stress corrosion cracking (SCC) test in high temperature high pressure water of reactor environment were investigated by two-dimensional and three-dimensional (3D) characterization in order to expose the mechanism that GB-engineering mitigates intergranular SCC. The 3D microstructure shown that the essential characteristic of the GB-engineered microstructure is formation of many large twin-boundaries as a result of multiple-twinning, which results in the formation of large grain-clusters. The large grain-clusters played a key role to the improvement of intergranular SCC resistance by GB-engineering. The main intergranular cracks propagated in a zigzag along the outer boundaries of these large grain-clusters because all inner boundaries of the grain-clusters were twin-boundaries (∑3) or twin-related boundaries (∑3n) which had much lower susceptibility to SCC than random boundaries. These large grain-clusters had tree-ring-shaped topology structure and very complex morphology. They got tangled so that difficult to be separated during SCC, resulting in some large crack-bridges retained in the crack surface.

Characterization of beta phase growth and experimental validation of long term thermal exposure sensitization of AA5XXX alloys

NASA Astrophysics Data System (ADS)

Zhu, Yakun

The United States Navy has a need for fast, light-weight ships to provide rapid deployment in its operations. Strong and corrosion-resistant aluminum alloys, such as AA5083 (UNS A95083) as well as other AA5XXX alloys, have properties that are well-suited for such applications. However, AA5XXX alloys are susceptible to intergranular corrosion (IGC) and stress corrosion cracking (SCC) because of sensitization which is a consequence of the formation of the grain boundary beta-phase, Al3Mg2, and the anodic dissolution of the beta-phase. Significant research has been performed to measure and understand the effects of time, temperature, stress, and sea water on sensitization and associated intergranular corrosion and stress corrosion cracking under steady-state conditions. In the present work, the behaviors of beta-phase nucleation and growth were characterized using optical and electron microscopy, the relationship between preexisting particles and beta-phase, as well as the effect of different heat treatment times and temperatures on IGC and SCC susceptibility of 5XXX alloys were investigated. Grain boundary beta-phase thickness was measured with high resolution transmission electron microscopy (TEM). The corrosion sensitization susceptibility was evaluated according to the American Society for Testing and Materials (ASTM) standard G67 tests, that is, nitric acid mass-loss testing (NAMLT). Diffusion of Mg is manifested by the thickening of beta-phase along the grainboundary because the grain boundary is considered as the preferential site for beta-phase nucleation. The beta-phase growth rate was monitored using high resolution TEM. The variety of precipitates and their subsequent effects on beta-phase nucleation and growth kinetics was investigated. The existence of various intermetallic particles was observed in both baseline and thermally exposed (70°C and 175°C) samples. These particles are usually either rod-shaped or equiaxed, and rich in Mn, Fe, and Cr. Indexing of lattice planes observed in a few of these particles suggested the composition is Al6Mn or Al6(Mn, Fe, Cr). This research also shows that the beta-phase precipitation occurs between the preexisting Mn rich particles. The basic model for the determination of diffusivity values, the prediction of beta-phase thickness growth, and corrosion sensitization prediction have been improved by new data from this research.

A comparative study of Sm networks in Al-10 at.%Sm glass and associated crystalline phases

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

Lv, Xiaobao; Ye, Zhuo; Sun, Yang

Here, the Al–Sm system is selected as a model system to study the transition process from liquid and amorphous to crystalline states. In recent work, we have shown that, in addition to long-range translational periodicity, crystal structures display well-defined short-range local atomic packing motifs that transcends liquid, amorphous and crystalline states. In this paper, we investigate the longer range spatial packing of these short-range motifs by studying the interconnections of Sm–Sm networks in different amorphous and crystalline samples obtained from molecular dynamics simulations. In our analysis, we concentrate on Sm–Sm distances in the range ~5.0–7.2 Å, corresponding to Sm atomsmore » in the second and third shells of Sm-centred clusters. We discover a number of empirical rules characterising the evolution of Sm networks from the liquid and amorphous states to associated metastable crystalline phases experimentally observed in the initial stages of devitrification of different amorphous samples. As direct simulation of glass formation is difficult because of the vast difference between experimental quench rates and what is achievable on the computer, we hope these rules will be helpful in building a better picture of structural evolution during glass formation as well as a more detailed description of phase selection and growth during devitrification.« less

A comparative study of Sm networks in Al-10 at.%Sm glass and associated crystalline phases

DOE PAGES

Lv, Xiaobao; Ye, Zhuo; Sun, Yang; ...

2018-04-03

Here, the Al–Sm system is selected as a model system to study the transition process from liquid and amorphous to crystalline states. In recent work, we have shown that, in addition to long-range translational periodicity, crystal structures display well-defined short-range local atomic packing motifs that transcends liquid, amorphous and crystalline states. In this paper, we investigate the longer range spatial packing of these short-range motifs by studying the interconnections of Sm–Sm networks in different amorphous and crystalline samples obtained from molecular dynamics simulations. In our analysis, we concentrate on Sm–Sm distances in the range ~5.0–7.2 Å, corresponding to Sm atomsmore » in the second and third shells of Sm-centred clusters. We discover a number of empirical rules characterising the evolution of Sm networks from the liquid and amorphous states to associated metastable crystalline phases experimentally observed in the initial stages of devitrification of different amorphous samples. As direct simulation of glass formation is difficult because of the vast difference between experimental quench rates and what is achievable on the computer, we hope these rules will be helpful in building a better picture of structural evolution during glass formation as well as a more detailed description of phase selection and growth during devitrification.« less

Multi-level storage and ultra-high speed of superlattice-like Ge50Te50/Ge8Sb92 thin film for phase-change memory application.

PubMed

Wu, Weihua; Chen, Shiyu; Zhai, Jiwei; Liu, Xinyi; Lai, Tianshu; Song, Sannian; Song, Zhitang

2017-10-06

Superlattice-like Ge 50 Te 50 /Ge 8 Sb 92 (SLL GT/GS) thin film was systematically investigated for multi-level storage and ultra-fast switching phase-change memory application. In situ resistance measurement indicates that SLL GT/GS thin film exhibits two distinct resistance steps with elevated temperature. The thermal stability of the amorphous state and intermediate state were evaluated with the Kissinger and Arrhenius plots. The phase-structure evolution revealed that the amorphous SLL GT/GS thin film crystallized into rhombohedral Sb phase first, then the rhombohedral GeTe phase. The microstructure, layered structure, and interface stability of SLL GT/GS thin film was confirmed by using transmission electron microscopy. The transition speed of crystallization and amorphization was measured by the picosecond laser pump-probe system. The volume variation during the crystallization was obtained from x-ray reflectivity. Phase-change memory (PCM) cells based on SLL GT/GS thin film were fabricated to verify the multi-level switching under an electrical pulse as short as 30 ns. These results illustrate that the SLL GT/GS thin film has great potentiality in high-density and high-speed PCM applications.

Heavy ion irradiations on synthetic hollandite-type materials: Ba1.0Cs0.3A2.3Ti5.7O16 (A=Cr, Fe, Al)

NASA Astrophysics Data System (ADS)

Tang, Ming; Tumurugoti, Priyatham; Clark, Braeden; Sundaram, S. K.; Amoroso, Jake; Marra, James; Sun, Cheng; Lu, Ping; Wang, Yongqiang; Jiang, Ying.-Bing.

2016-07-01

The hollandite supergroup of minerals has received considerable attention as a nuclear waste form for immobilization of Cs. The radiation stability of synthetic hollandite-type compounds described generally as Ba1.0Cs0.3A2.3Ti5.7O16 (A=Cr, Fe, Al) were evaluated by heavy ion (Kr) irradiations on polycrystalline single phase materials and multiphase materials incorporating the hollandite phases. Ion irradiation damage effects on these samples were examined using grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). Single phase compounds possess tetragonal structure with space group I4/m. GIXRD and TEM observations revealed that 600 keV Kr irradiation-induced amorphization on single phase hollandites compounds occurred at a fluence between 2.5×1014 Kr/cm2 and 5×1014 Kr/cm2. The critical amorphization fluence of single phase hollandite compounds obtained by in situ 1 MeV Kr ion irradiation was around 3.25×1014 Kr/cm2. The hollandite phase exhibited similar amorphization susceptibility under Kr ion irradiation when incorporated into a multiphase system.

Nuclear magnetic resonance analysis and activation energy spectrum of the irreversible structural relaxation of amorphous zirconium tungstate

NASA Astrophysics Data System (ADS)

Miotto, F.; Rech, G. L.; Turatti, A. M.; Catafesta, J.; Zorzi, J. E.; Pereira, A. S.; Perottoni, C. A.

2018-03-01

Zirconium tungstate undergoes a sequence of phase transitions from cubic (α -ZrW2O8 ) to orthorhombic (γ -ZrW2O8 ) to amorphous (a -ZrW2O8 ) upon increasing pressure at room temperature. The amorphous phase is known to undergo anomalous endothermic recrystallization into a high-temperature β -ZrW2O8 phase above 600∘C at ambient pressure (and back to α -ZrW2O8 when brought to room temperature). The endothermic recrystallization of a -ZrW2O8 is preceded by an irreversible exothermic structural relaxation. New W-O bonds are formed upon amorphization, continuing a tendency of increasing W coordination number in going from α to γ -ZrW2O8 . In fact, contrarily to α -ZrW2O8 , in which one-quarter of the oxygen atoms are bonded only to one W (terminal oxygens), previous works found no evidence of single-bonded oxygen atoms in a -ZrW2O8 . It thus could be argued that the irreversible character of the structural relaxation of a -ZrW2O8 is due to W-O bond breaking upon annealing of the amorphous phase. To test this hypothesis, x-ray diffraction, 17O magic-angle spinning NMR, Raman, and far-infrared analyses were performed on samples of amorphous zirconium tungstate previously annealed to increasingly higher temperatures, looking for any evidence of features that could be assigned to the presence of terminal oxygen atoms. No evidence of single-bonded oxygen was found before the onset of recrystallization. Furthermore, the kinetics of the structural relaxation of a -ZrW2O8 is consistent with a continuous spectrum of activation energy, spanning all the range from 1 to 2.5 eV . These findings suggest that the structural relaxation of amorphous zirconium tungstate, however irreversible, is not accompanied by W-O bond breaking, but most probably characterized by a succession of (mostly) irreversible local atomic rearrangements.

Atomic structure and pressure-induced phase transformations in a phase-change alloy

NASA Astrophysics Data System (ADS)

Xu, Ming

Phase-change materials exist in at least two phases under the ambient condition. One is the amorphous state and another is crystalline phase. These two phases have vastly different physical properties, such as electrical conductivity, optical reflectivity, mass density, thermal conductivity, etc. The distinct physical properties and the fast transformation between amorphous and crystalline phases render these materials the ability to store information. For example, the DVD and the Blue-ray discs take advantage of the optical reflectivity contrast, and the newly developed solid-state memories make use of the large conductivity difference. In addition, both the amorphous and crystalline phases in phase-change memories (PCMs) are very stable at room temperature, and they are easy to be scaled up in the production of devices with large storage density. All these features make phase-change materials the ideal candidates for the next-generation memories. Despite of the fast development of these new memory materials in industry, many fundamental physics problems underlying these interesting materials are still not fully resolved. This thesis is aiming at solving some of the key issues in phase-change materials. Most of phase-change materials are composed of Ge-Sb-Te constituents. Among all these Ge-Sb-Te based materials, Ge2Sb2Te5 (GST) has the best performance and has been frequently studied as a prototypical phase-change material. The first and foremost issue is the structure of the two functioning phases. In this thesis, we investigate the unique atomic structure and bonding nature of amorphous GST (a-GST) and crystalline GST ( c-GST), using ab initio tools and X-ray diffraction (XRD) methods. Their local structures and bonding scenarios are then analyzed using electronic structure calculations. In order to gain insight into the fast phase transformation mechanism, we also carried out a series of high-pressure experiments on GST. Several new polymorphs and their transformations have been revealed under high pressure via in situ XRD and in situ electrical resistivity measurements. The mechanisms of the structural and property changes have been uncovered via ab initio molecular dynamics simulations.

Theoretical studies on the mechanical behavior of granular materials under very low intergranular stresses

NASA Technical Reports Server (NTRS)

French, Kenneth W., Jr.

1986-01-01

The salient aspects of the theoretical modeling of a conventional triaxial test (CTC) of a cohesionless granular medium with stress and strain rate loading are described. Included are a controllable gravitational body force and provision for low confining pressure and/or very low intergranular stress. The modeling includes rational, analytic, and numerical phases, all in various stages of development. The numerical evolutions of theoretical models will be used in final design stages and in the analysis of the experimental data. In this the experimental design stage, it is of special interest to include in the candidate considerations every anomaly found in preliminary terrestrial experimentation. Most of the anomalies will be eliminated by design or enhanced for measurement as the project progresses. The main aspect of design being not the physical apparatus but the type and trajectories of loading elected. The major considerations that have been treated are: appearance and growth of local surface aberrations, stress-power coefficients, strain types, optical strain, radial bead migration, and measures of rotation for the proper stress flux.

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI{sub 4}

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

Liu, H.; Tse, J. S., E-mail: john.tse@usask.ca; Hu, M. Y.

2015-10-28

The pressure-induced amorphization and subsequent recrystallization of SnI{sub 4} have been investigated using first principles molecular dynamics calculations together with high-pressure {sup 119}Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI{sub 4} under ambient conditions. Although high pressure structures of SnI{sub 4} were thought to be determined by randommore » packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.« less

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of Snl 4

DOE PAGES

Liu, Hanyu; Tse, John S.; Hu, Michael Y.; ...

2015-10-27

The pressure-induced amorphization and subsequent recrystallization of SnI 4 have been investigated using first principles molecular dynamics calculations together with high-pressure 119Sn nuclear resonant inelastic x-ray scattering measurements. Above ~8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ~64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI 4 under ambient conditions. Although high pressure structures of SnI 4 were thought to be determined by random packingmore » of equal-sized spheres, we detected electron charge transfer in each phase. As a result, this charge transfer results in a crystal structure packing determined by larger than expected iodine atoms. (C) 2015 AIP Publishing LLC.« less

Impact of amorphization on the electronic properties of Zn-Ir-O systems.

PubMed

Muñoz Ramo, David; Bristowe, Paul D

2016-09-01

We analyze the geometry and electronic structure of a series of amorphous Zn-Ir-O systems using classical molecular dynamics followed by density functional theory taking into account two different charge states of Ir (+3 and  +4). The structures obtained consist of a matrix of interconnected metal-oxygen polyhedra, with Zn adopting preferentially a coordination of 4 and Ir a mixture of coordinations between 4 and 6 that depend on the charge state of Ir and its concentration. The amorphous phases display reduced band gaps compared to crystalline ZnIr2O4 and exhibit localized states near the band edges, which harm their transparency and hole mobility. Increasing amounts of Ir in the Ir(4+) phases decrease the band gap further while not altering it significantly in the Ir(3+) phases. The results are consistent with recent transmittance and resistivity measurements.

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI4.

PubMed

Liu, H; Tse, J S; Hu, M Y; Bi, W; Zhao, J; Alp, E E; Pasternak, M; Taylor, R D; Lashley, J C

2015-10-28

The pressure-induced amorphization and subsequent recrystallization of SnI4 have been investigated using first principles molecular dynamics calculations together with high-pressure (119)Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4 under ambient conditions. Although high pressure structures of SnI4 were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.

Nanoscale Transforming Mineral Phases in Fresh Nacre.

PubMed

DeVol, Ross T; Sun, Chang-Yu; Marcus, Matthew A; Coppersmith, Susan N; Myneni, Satish C B; Gilbert, Pupa U P A

2015-10-21

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropod shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.

Amorphization of cobalt monoxide nanocrystals and related explosive gas sensing applications.

PubMed

Li, L H; Xiao, J; Yang, G W

2015-10-16

Amorphous nanomaterials have attracted attention due to their excellent performances, highly comparable to their crystalline counterparts. Sensor materials with amorphous phases are usually evaluated to be unsuitable for sensors because of poor performance. As a matter of fact, amorphous nanomaterials have rather unique sensor behaviors. Here, we report the amorphousization of cobalt monoxide (CoO) nanocrystals driven by a unique process involved in laser ablation in liquid (LAL). We also established that a fast and nonequilibrium process created by LAL results in the amorphousization of nanocrystals. The as-prepared amorphous CoO (a-CoO) nanoflakes possess a high aspect ratio, which showed good sensing of explosive gases. The fabricated gas sensor can detect CO and H2 at levels as low as 5 and 10 ppm, respectively, at 100 °C. The performance characteristics of this sensor, including high sensitivity, low working temperature, and low detection limit, are superior to those of sensors made with crystalline phase oxides. Meanwhile, a temperature-dependent p-n transition was observed in the sensor's response to CO, suggesting that the sensing properties can be tailored by changing the carrier type, thus tuning the selectivity of sensors to different gases. These findings demonstrate the potential applications of amorphous nanomaterials as gas sensor components.

Viscous friction between crystalline and amorphous phase of dragline silk.

PubMed

Patil, Sandeep P; Xiao, Senbo; Gkagkas, Konstantinos; Markert, Bernd; Gräter, Frauke

2014-01-01

The hierarchical structure of spider dragline silk is composed of two major constituents, the amorphous phase and crystalline units, and its mechanical response has been attributed to these prime constituents. Silk mechanics, however, might also be influenced by the resistance against sliding of these two phases relative to each other under load. We here used atomistic molecular dynamics (MD) simulations to obtain friction forces for the relative sliding of the amorphous phase and crystalline units of Araneus diadematus spider silk. We computed the coefficient of viscosity of this interface to be in the order of 10(2) Ns/m(2) by extrapolating our simulation data to the viscous limit. Interestingly, this value is two orders of magnitude smaller than the coefficient of viscosity within the amorphous phase. This suggests that sliding along a planar and homogeneous surface of straight polyalanine chains is much less hindered than within entangled disordered chains. Finally, in a simple finite element model, which is based on parameters determined from MD simulations including the newly deduced coefficient of viscosity, we assessed the frictional behavior between these two components for the experimental range of relative pulling velocities. We found that a perfectly relative horizontal motion has no significant resistance against sliding, however, slightly inclined loading causes measurable resistance. Our analysis paves the way towards a finite element model of silk fibers in which crystalline units can slide, move and rearrange themselves in the fiber during loading.

Viscous Friction between Crystalline and Amorphous Phase of Dragline Silk

PubMed Central

Patil, Sandeep P.; Xiao, Senbo; Gkagkas, Konstantinos; Markert, Bernd; Gräter, Frauke

2014-01-01

The hierarchical structure of spider dragline silk is composed of two major constituents, the amorphous phase and crystalline units, and its mechanical response has been attributed to these prime constituents. Silk mechanics, however, might also be influenced by the resistance against sliding of these two phases relative to each other under load. We here used atomistic molecular dynamics (MD) simulations to obtain friction forces for the relative sliding of the amorphous phase and crystalline units of Araneus diadematus spider silk. We computed the coefficient of viscosity of this interface to be in the order of 102 Ns/m2 by extrapolating our simulation data to the viscous limit. Interestingly, this value is two orders of magnitude smaller than the coefficient of viscosity within the amorphous phase. This suggests that sliding along a planar and homogeneous surface of straight polyalanine chains is much less hindered than within entangled disordered chains. Finally, in a simple finite element model, which is based on parameters determined from MD simulations including the newly deduced coefficient of viscosity, we assessed the frictional behavior between these two components for the experimental range of relative pulling velocities. We found that a perfectly relative horizontal motion has no significant resistance against sliding, however, slightly inclined loading causes measurable resistance. Our analysis paves the way towards a finite element model of silk fibers in which crystalline units can slide, move and rearrange themselves in the fiber during loading. PMID:25119288

Mineralogy of Sediments on a Cold and Icy Early Mars

NASA Astrophysics Data System (ADS)

Rampe, E. B.; Horgan, B. H. N.; Smith, R.; Scudder, N.; Rutledge, A. M.; Bamber, E.; Morris, R. V.

2017-12-01

The water-related minerals discovered in ancient martian terrains suggest liquid water was abundant on the surface and/or near subsurface during Mars' early history. The debate remains, however, whether these minerals are indicative of a warm and wet or cold and icy climate. To characterize mineral assemblages of cold and icy mafic terrains, we analyzed pro- and supraglacial rocks and sediments from the Collier and Diller glacial valleys in Three Sisters, Oregon. We identified primary and secondary phases using X-ray diffraction (XRD), scanning and transmission electron microscopies with energy dispersive spectroscopy (SEM, TEM, EDS), and visible/short-wave-infrared (VSWIR) and thermal-infrared (TIR) spectroscopies. Samples from both glacial valleys are dominated by primary igneous minerals (i.e., plagioclase and pyroxene). Sediments in the Collier glacial valley contain minor to trace amounts of phyllosilicates and zeolites, but these phases are likely detrital and sourced from hydrothermally altered units on North Sister. We find that the authigenic phases in cold and icy mafic terrains are poorly crystalline and/or amorphous. TEM-EDS analyses of the <2 um size fraction of glacial flour shows the presence of many different nanophase materials, including iron oxides, devitrified volcanic glass, and Fe-Si-Al (e.g., proto-clay) phases. A variety of primary and secondary amorphous materials (e.g., volcanic glass, leached glass, allophane) have been suggested from orbital IR data from Mars, and the CheMin XRD on the Curiosity rover has identified X-ray amorphous materials in all rocks and soils measured to date. The compositions of the Gale Crater amorphous components cannot be explained by primary volcanic glass alone and likely include secondary silicates, iron oxides, and sulfates. We suggest that the prevalence of amorphous materials on the martian surface and the variety of amorphous components may be a signature of a cold and icy climate on Early Mars.

The use of inverse phase gas chromatography to measure the surface energy of crystalline, amorphous, and recently milled lactose.

PubMed

Newell, H E; Buckton, G; Butler, D A; Thielmann, F; Williams, D R

2001-05-01

To assess differences in surface energy due to processing induced disorder and to understand whether the disorder dominated the surfaces of particles. Inverse gas chromatography was used to compare the surface energies of crystalline, amorphous, and ball milled lactose. The milling process made ca 1% of the lactose amorphous, however the dispersive contribution to surface energy was 31.2, 37.1, and 41.6 mJ m(-2) for crystalline, spray dried and milled lactose, respectively. A physical mixture of crystalline (99%) and amorphous (1%) material had a dispersive surface energy of 31.5 mJ m(-2). Milling had made the surface energy similar to that of the amorphous material in a manner that was very different to a physical mixture of the same amorphous content. The milled material will have similar interfacial interactions to the 100% amorphous material.

Diffusion-coupled cohesive interface simulations of stress corrosion intergranular cracking in polycrystalline materials

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

Pu, Chao; Gao, Yanfei; Wang, Yanli

To study the stress corrosion intergranular cracking mechanism, a diffusion-coupled cohesive zone model (CZM) is proposed for the simulation of the stress-assisted diffusional process along grain boundaries and the mechanical response of grain boundary sliding and separation. This simulation methodology considers the synergistic effects of impurity diffusion driven by pressure gradient and degradation of grain boundary strength by impurity concentration. The diffusion-coupled CZM is combined with crystal plasticity finite element model (CPFEM) to simulate intergranular fracture of polycrystalline material under corrosive environment. Significant heterogeneity of the stress field and extensive impurity accumulation is observed at grain boundaries and junction points.more » Deformation mechanism maps are constructed with respect to the grain boundary degradation factor and applied strain rate, which dictate the transition from internal to near-surface intergranular fracture modes under various strain amplitudes and grain sizes.« less

Continuous and line spectra of granules and intergranular lanes

NASA Astrophysics Data System (ADS)

Suemoto, Z.; Hiei, E.; Nakagomi, Y.

1990-05-01

Temperature and velocity structures above granules and intergranular lanes were studied on spectrograms covering Ca II H and K lines. In agreement with earlier results, it was confirmed more quantitatively that there appear two kinds of bright continua, one in the outer wings (granular continuum) and the other in the inner wings (temporarily called K0-continuum) of Ca II H and K lines, and that these two kinds of bright continua are located more or less in a complementary fashion. Further, it was found that the bright K0-continuum is well associated with higher central residual intensity of absorption lines. These facts suggest that, in the upper photosphere, there are high temperature regions in the intergranular lanes. Motions above granular regions are essentially upwards, whereas those of intergranular regions are predominantly downwards, and in the uppermost photosphere the motions become more random.

Structural Inheritance and Redox Performance of Nanoporous Electrodes from Nanocrystalline Fe85.2B10-14P0-4Cu0.8 Alloys

PubMed Central

Fu, Chaoqun; Xu, Lijun; Dan, Zhenhua; Makino, Akihiro; Hara, Nobuyoshi; Qin, Fengxiang; Chang, Hui

2017-01-01

Nanoporous electrodes have been fabricated by selectively dissolving the less noble α-Fe crystalline phase from nanocrystalline Fe85.2B14–xPxCu0.8 alloys (x= 0, 2, 4 at.%). The preferential dissolution is triggered by the weaker electrochemical stability of α-Fe nanocrystals than amorphous phase. The final nanoporous structure is mainly composed of amorphous residual phase and minor undissolved α-Fe crystals and can be predicted from initial microstructure of nanocrystalline precursor alloys. The structural inheritance is proved by the similarity of the size and outlines between nanopores formed after dealloying in 0.1 M H2SO4 and α-Fe nanocrystals precipitated after annealing of amorphous Fe85.2B14−xPxCu0.8 (x = 0, 2, 4 at.%) alloys. The Redox peak current density of the nanoporous electrodes obtained from nanocrystalline Fe85.2B10P4Cu0.8 alloys is more than one order higher than those of Fe plate electrode and its counterpart nanocrystalline alloys due to the large surface area and nearly-amorphous nature of ligaments. PMID:28594378

Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean

PubMed Central

Tao, Jinhui; Zhou, Dongming; Zhang, Zhisen; Xu, Xurong; Tang, Ruikang

2009-01-01

Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue. However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization. Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired lesson from nature, which can be developed into an advanced strategy to control material fabrications. PMID:20007788

Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean.

PubMed

Tao, Jinhui; Zhou, Dongming; Zhang, Zhisen; Xu, Xurong; Tang, Ruikang

2009-12-29

Many animals such as crustacean periodically undergo cyclic molt of the exoskeleton. During this process, amorphous calcium mineral phases are biologically stabilized by magnesium and are reserved for the subsequent rapid formation of new shell tissue. However, it is a mystery how living organisms can regulate the transition of the precursor phases precisely. We reveal that the shell mineralization from the magnesium stabilized precursors is associated with the presence of Asp-rich proteins. It is suggested that a cooperative effect of magnesium and Asp-rich compound can result into a crystallization switch in biomineralization. Our in vitro experiments confirm that magnesium increases the lifetime of amorphous calcium carbonate and calcium phosphate in solution so that the crystallization can be temporarily switched off. Although Asp monomer alone inhibits the crystallization of pure amorphous calcium minerals, it actually reduces the stability of the magnesium-stabilized precursors to switch on the transformation from the amorphous to crystallized phases. These modification effects on crystallization kinetics can be understood by an Asp-enhanced magnesium desolvation model. The interesting magnesium-Asp-based switch is a biologically inspired lesson from nature, which can be developed into an advanced strategy to control material fabrications.

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

Vasileiadis, Thomas; Department of Materials Science, University of Patras, GR-26504 Rio-Patras; Yannopoulos, Spyros N., E-mail: sny@iceht.forth.gr

Controlled photo-induced oxidation and amorphization of elemental trigonal tellurium are achieved by laser irradiation at optical wavelengths. These processes are monitored in situ by time-resolved Raman scattering and ex situ by electron microscopies. Ultrathin TeO₂ films form on Te surfaces, as a result of irradiation, with an interface layer of amorphous Te intervening between them. It is shown that irradiation, apart from enabling the controllable transformation of bulk Te to one-dimensional nanostructures, such as Te nanotubes and hybrid core-Te/sheath-TeO₂ nanowires, causes also a series of light-driven (athermal) phase transitions involving the crystallization of the amorphous TeO₂ layers and its transformationmore » to a multiplicity of crystalline phases including the γ-, β-, and α-TeO₂ crystalline phases. The kinetics of the above photo-induced processes is investigated by Raman scattering at various laser fluences revealing exponential and non-exponential kinetics at low and high fluence, respectively. In addition, the formation of ultrathin (less than 10 nm) layers of amorphous TeO₂ offers the possibility to explore structural transitions in 2D glasses by observing changes in the short- and medium-range structural order induced by spatial confinement.« less

Formation of nanotwin networks during high-temperature crystallization of amorphous germanium

DOE PAGES

Sandoval, Luis; Reina, Celia; Marian, Jaime

2015-11-26

Germanium is an extremely important material used for numerous functional applications in many fields of nanotechnology. In this paper, we study the crystallization of amorphous Ge using atomistic simulations of critical nano-metric nuclei at high temperatures. We find that crystallization occurs by the recurrent transfer of atoms via a diffusive process from the amorphous phase into suitably-oriented crystalline layers. We accompany our simulations with a comprehensive thermodynamic and kinetic analysis of the growth process, which explains the energy balance and the interfacial growth velocities governing grain growth. For the <111> crystallographic orientation, we find a degenerate atomic rearrangement process, withmore » two zero-energy modes corresponding to a perfect crystalline structure and the formation of a Σ3 twin boundary. Continued growth in this direction results in the development a twin network, in contrast with all other growth orientations, where the crystal grows defect-free. This particular mechanism of crystallization from amorphous phases is also observed during solid-phase epitaxial growth of <111> semiconductor crystals, where growth is restrained to one dimension. Lastly, we calculate the equivalent X-ray diffraction pattern of the obtained nanotwin networks, providing grounds for experimental validation.« less

Amorphous layer formation in Al86.0Co7.6Ce6.4 glass-forming alloy by large-area electron beam irradiation

NASA Astrophysics Data System (ADS)

Li, C. L.; Murray, J. W.; Voisey, K. T.; Clare, A. T.; McCartney, D. G.

2013-09-01

Amorphous Al-Co-Ce alloys are of interest because of their resistance to corrosion, but high cooling rates are generally required to suppress the formation of crystalline phases. In this study, the surface of a bulk crystalline Al-Co-Ce alloy of a glass-forming composition was treated using large area electron beam (LAEB) irradiation. Scanning electron microscopy shows that, compared to the microstructure of the original crystalline material, the treated surface exhibits greatly improved microstructural and compositional uniformity. Glancing angle X-ray diffraction conducted on the surface of treated samples indicates the formation of the amorphous phase following 25 and 50 pulses at 35 kV cathode voltage. However, when the samples are treated with 100 and 150 pulses at 35 kV cathode voltage of electron beam irradiation, the treated layer comprises localised crystalline regions in an amorphous matrix. In addition, the formation of cracks in the treated layer is found to be localised around the Al8Co2Ce phase in the bulk material. Overall, crack length per unit area had no clear change with an increase in the number of pulses.

Formation of Nanotwin Networks during High-Temperature Crystallization of Amorphous Germanium

PubMed Central

Sandoval, Luis; Reina, Celia; Marian, Jaime

2015-01-01

Germanium is an extremely important material used for numerous functional applications in many fields of nanotechnology. In this paper, we study the crystallization of amorphous Ge using atomistic simulations of critical nano-metric nuclei at high temperatures. We find that crystallization occurs by the recurrent transfer of atoms via a diffusive process from the amorphous phase into suitably-oriented crystalline layers. We accompany our simulations with a comprehensive thermodynamic and kinetic analysis of the growth process, which explains the energy balance and the interfacial growth velocities governing grain growth. For the 〈111〉 crystallographic orientation, we find a degenerate atomic rearrangement process, with two zero-energy modes corresponding to a perfect crystalline structure and the formation of a Σ3 twin boundary. Continued growth in this direction results in the development a twin network, in contrast with all other growth orientations, where the crystal grows defect-free. This particular mechanism of crystallization from amorphous phases is also observed during solid-phase epitaxial growth of 〈111〉 semiconductor crystals, where growth is restrained to one dimension. We calculate the equivalent X-ray diffraction pattern of the obtained nanotwin networks, providing grounds for experimental validation. PMID:26607496

Bonding structure in amorphous carbon nitride: A spectroscopic and nuclear magnetic resonance study

NASA Astrophysics Data System (ADS)

Sánchez-López, J. C.; Donnet, C.; Lefèbvre, F.; Fernández-Ramos, C.; Fernández, A.

2001-07-01

Since the prediction of Liu and Cohen [Science 245, 841 (1989)] of the potential extraordinary mechanical properties of crystalline β-C3N4, many authors have attempted its synthesis. However, in most cases, the obtained materials are amorphous phases with a complex bonding structure. Their characterization is complicated due to the absence of a reference compound, the lack of long-range order, and the poor knowledge about their bonding structure. In this article, we present 1H, 13C, and 15N solid-state nuclear magnetic resonance (NMR) measurements for the determination of the bonding types in amorphous CNx films. NMR measurements do not require long-range order and are able to clearly identify the signals from the sp2- and sp3-bonded phases. The analysis of the data obtained by other characterization techniques, such as infrared spectroscopy, x-ray photoelectron spectroscopy, electron energy-loss spectroscopy, and x-ray absorption near-edge spectroscopy on the same sample, based on the information acquired by NMR, enables the description of a structure model for the studied amorphous-CNx phase prepared by dc-magnetron sputtering and to revise the interpretation found in the literature.

Neutron irradiation and high temperature effects on amorphous Fe-based nano-coatings on steel – A macroscopic assessment

DOE PAGES

Simos, N.; Zhong, Z.; Dooryhee, E.; ...

2017-03-23

Here, this study revealed that loss of ductility in an amorphous Fe-alloy coating on a steel substrate composite structure was essentially prevented from occurring, following radiation with modest neutron doses of ~2 x 10 18 n/cm 2. At the higher neutron dose of ~2 x 10 19, macroscopic stress-strain analysis showed that the amorphous Fe-alloy nanostructured coating, while still amorphous, experienced radiation-induced embrittlement, no longer offering protection against ductility loss in the coating-substrate composite structure. Neutron irradiation in a corrosive environment revealed exemplary oxidation/corrosion resistance of the amorphous Fe-alloy coating, which is attributed to the formation of the Fe 2Bmore » phase in the coating. To establish the impact of elevated temperatures on the amorphous-to-crystalline transition in the amorphous Fe-alloy, electron microscopy was carried out which confirmed the radiation-induced suppression of crystallization in the amorphous Fe-alloy nanostructured coating.« less

Evolution of interphase and intergranular strain in zirconium-niobium alloys during deformation at room temperature

NASA Astrophysics Data System (ADS)

Cai, Song

Zr-2.5Nb is currently used for pressure tubes in the CANDU (CANada Deuterium Uranium) reactor. A complete understanding of the deformation mechanism of Zr-2.5Nb is important if we are to accurately predict the in-reactor performance of pressure tubes and guarantee normal operation of the reactors. This thesis is a first step in gaining such an understanding; the deformation mechanism of ZrNb alloys at room temperature has been evaluated through studying the effect of texture and microstructure on deformation. In-situ neutron diffraction was used to monitor the evolution of the lattice strain of individual grain families along both the loading and Poisson's directions and to track the development of interphase and intergranular strains during deformation. The following experiments were carried out with data interpreted using elasto-plastic modeling techniques: (1) Compression tests of a 100%betaZr material at room temperature. (2) Tension and compression tests of hot rolled Zr-2.5Nb plate material. (3) Compression of annealed Zr-2.5Nb. (4) Cyclic loading of the hot rolled Zr-2.5Nb. (5) Compression tests of ZrNb alloys with different Nb and oxygen contents. The experimental results were interpreted using a combination of finite element (FE) and elasto-plastic self-consistent (EPSC) models. The phase properties and phase interactions well represented by the FE model, the EPSC model successfully captured the evolution of intergranular constraint during deformation and provided reasonable estimates of the critical resolved shear stress and hardening parameters of different slip systems under different conditions. The consistency of the material parameters obtained by the EPSC model allows the deformation mechanism at room temperature and the effect of textures and microstructures of ZrNb alloys to be understood. This work provides useful information towards manufacturing of Zr-2.5Nb components and helps in producing ideal microstructures and material properties for pressure tubes. Also it is helpful in guiding the development of new materials for the next generation of nuclear reactors. Furthermore, the large data set obtained from this study can be used in evaluation and improving current and future polycrystalline deformation models.

International Conference Intergranular and Interphase Boundaries (9th) (IIB󈨦) Held in Prague, Czech Republic, 6 - 9 July 1998

DTIC Science & Technology

1998-07-09

exist only as isolated single crystalline "islands" in the " sea " of melted phase. Tw2=386.5"C 400 T_.1=381"C L S300 wl L 03. E I- 200 S(Zn) (Sn) 0 20 40...Physics, 142432 Chernogolovka, Moscow distr., Fax: +7(096) 576-41-11; E-mail: kisel@issp.ac.ru The study of microplasticity in alkali halides, metals and

Amorphous surface layers in Ti-implanted Fe

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

Knapp, J.A.; Follstaedt, D.M.; Picraux, S.T.

1979-01-01

Implanting Ti into high-purity Fe results in an amorphous surface layer which is composed of not only Fe and Ti, but also C. Implantations were carried out at room temperature over the energy range 90 to 190 keV and fluence range 1 to 2 x 10/sup 16/ at/cm/sup 2/. The Ti-implanted Fe system has been characterized using transmission electron microscopy (TEM), ion backscattering and channeling analysis, and (d,p) nuclear reaction analysis. The amorphous layer was observed to form at the surface and grow inward with increasing Ti fluence. For an implant of 1 x 10/sup 17/ Ti/cm/sup 2/ at 180more » keV the layer thickness was 150 A, while the measured range of the implanted Ti was approx. 550 A. This difference is due to the incorporation of C into the amorphous alloy by C being deposited on the surface during implantation and subsequently diffusing into the solid. Our results indicate that C is an essential constituent of the amorphous phase for Ti concentrations less than or equal to 10 at. %. For the 1 x 10/sup 17/ Ti/cm/sup 2/ implant, the concentration of C in the amorphous phase was approx. 25 at. %, while that of Ti was only approx. 3 at. %. A higher fluence implant of 2 x 10/sup 17/ Ti/cm/sup 2/ produced an amorphous layer with a lower C concentration of approx. 10 at. % and a Ti concentration of approx. 20 at. %.« less

Nonequilibrium Phase Transitions in Supercooled Water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2012-02-01

We present results of a simulation study of water driven out of equilibrium. Using transition path sampling, we can probe stationary path distributions parameterize by order parameters that are extensive in space and time. We find that by coupling external fields to these parameters, we can drive water through a first order dynamical phase transition into amorphous ice. By varying the initial equilibrium distributions we can probe pathways for the creation of amorphous ices of low and high densities.

Miscibility as a factor for component crystallization in multisolute frozen solutions.

PubMed

Izutsu, Ken-Ichi; Shibata, Hiroko; Yoshida, Hiroyuki; Goda, Yukihiro

2014-07-01

The relationship between the miscibility of formulation ingredients and their crystallization during the freezing segment of the lyophilization process was studied. The thermal properties of frozen solutions containing myo-inositol and cosolutes were obtained by performing heating scans from -70 °C before and after heat treatment at -20 °C to -5 °C. Addition of dextran 40,000 reduced and prevented crystallization of myo-inositol. In the first scan, some frozen solutions containing an inositol-rich mixture with dextran showed single broad transitions (Tg's: transition temperatures of maximally freeze-concentrated solutes) that indicated incomplete mixing of the concentrated amorphous solutes. Heat treatment of these frozen solutions induced separation of the solutes into inositol-dominant and solute mixture phases (Tg' splitting) following crystallization of myo-inositol (Tg' shifting). The crystal growth involved myo-inositol molecules in the solute mixture phase. The amorphous-amorphous phase separation and resulting loss of the heteromolecular interaction in the freeze-concentrated inositol-dominant phase should allow ordered assembly of the solute molecules required for nucleation. Some dextran-rich and intermediate concentration ratio frozen solutions retained single Tg's of the amorphous solute mixture, both before and after heat treatments. The relevance of solute miscibility on the crystallization of myo-inositol was also indicated in the systems containing glucose or recombinant human albumin. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Influence of deposition temperature and amorphous carbon on microstructure and oxidation resistance of magnetron sputtered nanocomposite Crsbnd C films

NASA Astrophysics Data System (ADS)

Nygren, Kristian; Andersson, Matilda; Högström, Jonas; Fredriksson, Wendy; Edström, Kristina; Nyholm, Leif; Jansson, Ulf

2014-06-01

It is known that mechanical and tribological properties of transition metal carbide films can be tailored by adding an amorphous carbon (a-C) phase, thus making them nanocomposites. This paper addresses deposition, microstructure, and for the first time oxidation resistance of magnetron sputtered nanocomposite Crsbnd C/a-C films with emphasis on studies of both phases. By varying the deposition temperature between 20 and 700 °C and alternating the film composition, it was possible to deposit amorphous, nanocomposite, and crystalline Crsbnd C films containing about 70% C and 30% Cr, or 40% C and 60% Cr. The films deposited at temperatures below 300 °C were X-ray amorphous and 500 °C was required to grow crystalline phases. Chronoamperometric polarization at +0.6 V vs. Ag/AgCl (sat. KCl) in hot 1 mM H2SO4 resulted in oxidation of Crsbnd C, yielding Cr2O3 and C, as well as oxidation of C. The oxidation resistance is shown to depend on the deposition temperature and the presence of the a-C phase. Physical characterization of film surfaces show that very thin C/Cr2O3/Crsbnd C layers develop on the present material, which can be used to improve the oxidation resistance of, e.g. stainless steel electrodes.

New transformations between crystalline and amorphous ice

NASA Technical Reports Server (NTRS)

Hemley, R. J.; Chen, L. C.; Mao, H. K.

1989-01-01

High-pressure optical and spectroscopic techniques were used to obtain directly the ice I(h) - hda-ice transformation in a diamond-anvil cell, and the stability of the amorphous form is examined as functions of pressure and temperature. It is demonstrated that hda-ice transforms abruptly at 4 GPa and 77 K to a crystalline phase close in structure to orientationally disordered ice-VII and to a more highly ordered, ice-VIII-like structure at higher temperatures. This is the first time that an amorphous solid is observed to convert to a crystalline solid at low temperatures by compression alone. Phase transitions of this type may be relevant on icy planetary satellites, and there may also be implications for the high-pressure behavior of silica.

The Effect of Shock on the Amorphous Component in Altered Basalt

NASA Technical Reports Server (NTRS)

Eckley, S. A.; Wright, S. P.; Rampe, E. B.; Niles, P. B.

2017-01-01

Investigation of the geochemical and mineralogical composition of the Martian surface provides insight into the geologic history of the predominantly basaltic crust. The Chemistry and Mineralogy (CheMin) instrument onboard the Curiosity rover has returned the first X-Ray diffraction data from the Martian surface. However, large proportions (27 +/- 14 with some estimates as high as 50 weight percentage) of an amorphous component have been reported. As a remedy to this problem, mass balance equations using geochemistry, volatile chemistry, and mineralogy have been employed to constrain the geochemistry of the amorphous component. However, "the nature and number of amorphous phases that constitute the amorphous component is not unequivocally known". Multiple hypotheses have been proposed to explain the origin of this amorphous component: Allophane (Al2O); Basaltic glass (Volcanic and impact); Palagonite (Altered basaltic glass); Hisingerite (Fe (sup 3 plus)-bearing phyllosilicate); S/Cl-rich component (sulfates and/or akaganeite); Nanophase ferric oxide component (npOx). Establishing a multi-phase amorphous component from a basaltic precursor that has undergone physical and chemical weathering within geochemical constraints is of paramount importance to better understand the composition of a large portion of the Martian surface (up to 50 weight percentage). Shocked basalts from Lonar Crater in India are valuable analogs for the Martian surface because it is a well-preserved impact crater in a basaltic target. Having undergone pre- and post-shock aqueous alteration, these rocks provide crucial data regarding the effect of shock on the amorphous component in altered basalt. By conducting mass balance equations similar to what has been performed for Gale crater materials, we attempt to calculate the geochemistry of the amorphous component in altered basalts ranging from unshocked to Class 5 (Table 1). This has the potential to reveal the nature and origin (i.e. primary igneous, shock metamorphic, and/or aqueous alteration occurring before or after the impact event) of the amorphous component in shocked basalt with the goal of unravelling the history of the Martian surface.

Low-temperature interface reactions in layered Au/Sb films: In situ investigation of the formation of an amorphous phase

NASA Astrophysics Data System (ADS)

Boyen, H.-G.; Cossy-Favre, A.; Oelhafen, P.; Siber, A.; Ziemann, P.; Lauinger, C.; Moser, T.; Häussler, P.; Baumann, F.

1995-01-01

Photoelectron-spectroscopy methods combined with electrical-resistance measurements were employed to study the effects of intermixing at Au/Sb interfaces at low temperatures. For the purpose of characterizing the growth processes of the intermixed phase on a ML scale, Au/Sb bilayers (layer thicknesses DAu=0.5-75 ML and DSb=150 ML) were evaporated at 77 K and the different in situ techniques allowed a comparison to vapor-quenched amorphous AuxSb100-x alloys. For Au thicknesses between 0.5 and 0.9 ML, a change from a semiconducting to a metallic behavior of the samples has been detected, as indicated by the development of a steplike photoelectron intensity at the Fermi level. Evidence has been found that for Au coverages <= 6 ML chemical reactions at the Au/Sb interface occur, leading to the formation of a homogeneously intermixed amorphous layer with a maximum thickness of about 2.3 nm and Au concentrations as high as x~=80 at. %. This latter value corresponds to the limiting Au content where amorphous alloys can be prepared at low temperature (0 at. % <=x<= 80 at. %). For nominal coverages beyond 6 ML polycrystalline Au films were formed. Consequently, Au/Sb multilayers with sufficiently small modulation lengths, which were prepared at 130 K by ion-beam sputtering, were observed to grow as a homogeneous amorphous phase over a broad range of compositions, as evidenced by in situ resistance measurements and by comparing the obtained crystallization temperatures to those of vapor-quenched amorphous alloys. Variation of the deposition temperature Ts revealed that an amorphous interface layer is only formed for Ts<= 220 K. This is consistent with the fact that for multilayers with large modulation lengths containing unreacted polycrystalline Au and Sb layers, long-range interdiffusion is found to set in at temperatures above 230 K. This interdiffusion, however, results in the formation of polycrystalline Au-Sb alloys.

From crystalline to amorphous calcium pyrophosphates: A solid state Nuclear Magnetic Resonance perspective.

PubMed

Gras, Pierre; Baker, Annabelle; Combes, Christèle; Rey, Christian; Sarda, Stéphanie; Wright, Adrian J; Smith, Mark E; Hanna, John V; Gervais, Christel; Laurencin, Danielle; Bonhomme, Christian

2016-02-01

Hydrated calcium pyrophosphates (CPP, Ca2P2O7·nH2O) are a fundamental family of materials among osteoarticular pathologic calcifications. In this contribution, a comprehensive multinuclear NMR (Nuclear Magnetic Resonance) study of four crystalline and two amorphous phases of this family is presented. (1)H, (31)P and (43)Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different (1)H and (43)Ca solid state NMR signatures were observed for the amorphous phases, depending on the synthetic procedure used. The NMR parameters of the crystalline phases were determined using the GIPAW (Gauge Including Projected Augmented Wave) DFT approach, based on first-principles calculations. In some cases, relaxed structures were found to improve the agreement between experimental and calculated values, demonstrating the importance of proton positions and pyrophosphate local geometry in this particular NMR crystallography approach. Such calculations serve as a basis for the future ab initio modeling of the amorphous CPP phases. The general concept of NMR crystallography is applied to the detailed study of calcium pyrophosphates (CPP), whether hydrated or not, and whether crystalline or amorphous. CPP are a fundamental family of materials among osteoarticular pathologic calcifications. Their prevalence increases with age, impacting on 17.5% of the population after the age of 80. They are frequently involved or associated with acute articular arthritis such as pseudogout. Current treatments are mainly directed at relieving the symptoms of joint inflammation but not at inhibiting CPP formation nor at dissolving these crystals. The combination of advanced NMR techniques, modeling and DFT based calculation of NMR parameters allows new original insights in the detailed structural description of this important class of biomaterials. Copyright © 2016. Published by Elsevier Ltd.

Electronic transport in mixed-phase hydrogenated amorphous/nanocrystalline silicon thin films

NASA Astrophysics Data System (ADS)

Wienkes, Lee Raymond

Interest in mixed-phase silicon thin film materials, composed of an amorphous semiconductor matrix in which nanocrystalline inclusions are embedded, stems in part from potential technological applications, including photovoltaic and thin film transistor technologies. Conventional mixed-phase silicon films are produced in a single plasma reactor, where the conditions of the plasma must be precisely tuned, limiting the ability to adjust the film and nanoparticle parameters independently. The films presented in this thesis are deposited using a novel dual-plasma co-deposition approach in which the nanoparticles are produced separately in an upstream reactor and then injected into a secondary reactor where an amorphous silicon film is being grown. The degree of crystallinity and grain sizes of the films are evaluated using Raman spectroscopy and X-ray diffraction respectively. I describe detailed electronic measurements which reveal three distinct conduction mechanisms in n-type doped mixed-phase amorphous/nanocrystalline silicon thin films over a range of nanocrystallite concentrations and temperatures, covering the transition from fully amorphous to ~30% nanocrystalline. As the temperature is varied from 470 to 10 K, we observe activated conduction, multiphonon hopping (MPH) and Mott variable range hopping (VRH) as the nanocrystal content is increased. The transition from MPH to Mott-VRH hopping around 100K is ascribed to the freeze out of the phonon modes. A conduction model involving the parallel contributions of these three distinct conduction mechanisms is shown to describe both the conductivity and the reduced activation energy data to a high accuracy. Additional support is provided by measurements of thermal equilibration effects and noise spectroscopy, both done above room temperature (>300 K). This thesis provides a clear link between measurement and theory in these complex materials.

Morphology and kinetics of crystals growth in amorphous films of Cr2O3, deposited by laser ablation

NASA Astrophysics Data System (ADS)

Bagmut, Aleksandr

2018-06-01

An electron microscopic investigation was performed on the structure and kinetics of the crystallization of amorphous Cr2O3 films, deposited by pulsed laser sputtering of chromium target in an oxygen atmosphere. The crystallization was initiated by the action of an electron beam on an amorphous film in the column of a transmission electron microscope. The kinetic curves were plotted on the basis of a frame-by-frame analysis of the video recorded during the crystallization of the film. It was found that the amorphous phase - crystal phase transition in Cr2O3 films occurs as a layer polymorphic crystallization and is characterized by the values of the dimensionless relative length unit δ0 ≈ 2000-3100. The action of the electron beam initiates the formation of crystals of two basic morphological forms: disk-shaped and sickle-shaped. Growth of a disk-shaped crystals is characterized by a constant rate v and the quadratic dependence of the fraction of the crystalline phase x on the time t. Sickle-shaped crystal at an initial stage, as it grows, becomes as ring-shaped and disk-shaped crystal. The growth of a sickle-shaped crystal is characterized by normal and tangential velocity components, which depend on the time as ∼√t and as ∼1/√t respectively The end point of the arc at the interface between the amorphous and crystalline phases as the crystal grows describes a curve, which is similar to the Fermat helix. For sickle-shaped, as well as for disk-shaped crystals, the degree of crystallinity x ∼ t2.

Electron-beam-irradiation-induced crystallization of amorphous solid phase change materials

NASA Astrophysics Data System (ADS)

Zhou, Dong; Wu, Liangcai; Wen, Lin; Ma, Liya; Zhang, Xingyao; Li, Yudong; Guo, Qi; Song, Zhitang

2018-04-01

The electron-beam-irradiation-induced crystallization of phase change materials in a nano sized area was studied by in situ transmission electron microscopy and selected area electron diffraction. Amorphous phase change materials changed to a polycrystalline state after being irradiated with a 200 kV electron beam for a long time. The results indicate that the crystallization temperature strongly depends on the difference in the heteronuclear bond enthalpy of the phase change materials. The selected area electron diffraction patterns reveal that Ge2Sb2Te5 is a nucleation-dominated material, when Si2Sb2Te3 and Ti0.5Sb2Te3 are growth-dominated materials.

Enhanced stability and local structure in biologically relevant amorphous materials containing pyrophosphate

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

Slater, Colin; Laurencin, Danielle; Burnell, Victoria

2012-10-25

There is increasing evidence that amorphous inorganic materials play a key role in biomineralisation in many organisms, however the inherent instability of synthetic analogues in the absence of the complex in vivo matrix limits their study and clinical exploitation. To address this, we report here an approach that enhances long-term stability to >1 year of biologically relevant amorphous metal phosphates, in the absence of any complex stabilizers, by utilizing pyrophosphates (P{sub 2}O{sub 7}{sup 4-}); species themselves ubiquitous in vivo. Ambient temperature precipitation reactions were employed to synthesise amorphous Ca{sub 2}P{sub 2}O{sub 7}.nH{sub 2}O and Sr{sub 2}P{sub 2}O{sub 7}.nH{sub 2}O (3.8more » < n < 4.2) and their stability and structure were investigated. Pair distribution functions (PDF) derived from synchrotron X-ray data indicated a lack of structural order beyond 8 {angstrom} in both phases, with this local order found to resemble crystalline analogues. Further studies, including {sup 1}H and {sup 31}P solid state NMR, suggest the unusually high stability of these purely inorganic amorphous phases is partly due to disorder in the P-O-P bond angles within the P{sub 2}O{sub 7} units, which impede crystallization, and to water molecules, which are involved in H-bonds of various strengths within the structures and hamper the formation of an ordered network. In situ high temperature powder X-ray diffraction data indicated that the amorphous nature of both phases surprisingly persisted to 450 C. Further NMR and TGA studies found that above ambient temperature some water molecules reacted with P{sub 2}O{sub 7} anions, leading to the hydrolysis of some P-O-P linkages and the formation of HPO{sub 4}{sup 2-} anions within the amorphous matrix. The latter anions then recombined into P{sub 2}O{sub 7} ions at higher temperatures prior to crystallization. Together, these findings provide important new materials with unexplored potential for enzyme-assisted resorption and establish factors crucial to isolate further stable amorphous inorganic materials.« less

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

NASA Astrophysics Data System (ADS)

McMillan, Paul F.; Gryko, Jan; Bull, Craig; Arledge, Richard; Kenyon, Anthony J.; Cressey, Barbara A.

2005-03-01

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr 2) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300 °C. Syntheses at higher temperatures gave rise to microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.

Direct-patterned optical waveguides on amorphous silicon films

DOEpatents

Vernon, Steve; Bond, Tiziana C.; Bond, Steven W.; Pocha, Michael D.; Hau-Riege, Stefan

2005-08-02

An optical waveguide structure is formed by embedding a core material within a medium of lower refractive index, i.e. the cladding. The optical index of refraction of amorphous silicon (a-Si) and polycrystalline silicon (p-Si), in the wavelength range between about 1.2 and about 1.6 micrometers, differ by up to about 20%, with the amorphous phase having the larger index. Spatially selective laser crystallization of amorphous silicon provides a mechanism for controlling the spatial variation of the refractive index and for surrounding the amorphous regions with crystalline material. In cases where an amorphous silicon film is interposed between layers of low refractive index, for example, a structure comprised of a SiO.sub.2 substrate, a Si film and an SiO.sub.2 film, the formation of guided wave structures is particularly simple.

Probing microstructure and phase evolution of α-MoO 3 nanobelts for sodium-ion batteries by in situ transmission electron microscopy

DOE PAGES

Xia, Weiwei; Xu, Feng; Zhu, Chongyang; ...

2016-07-15

The fundamental electrochemical reaction mechanisms and the phase transformation pathways of layer-structured α-MoO 3 nanobelt during the sodiation/desodiation process to date remain largely unknown. In this study, to observe the real-time sodiation/desodiaton behaviors of α-MoO 3 during electrochemical cycling, we construct a MoO 3 anode sodium-ion battery inside a transmission electron microscope (TEM). Utilizing in situ TEM and electron diffraction pattern (EDP) observation, α-MoO 3 nanobelts are found to undergo a unique multi-step phase transformation. Upon the first sodiation, α-MoO 3 nanobelts initially form amorphous Na xMoO3 phase and are subsequently sodiated into intermediate phase of crystalline NaMoO 2, finallymore » resulting in the crystallized Mo nanograins embedded within the Na 2O matrix. During the first desodiation process, Mo nanograins are firstly re-oxidized into intermediate phase NaMoO 2 that is further transformed into amorphous Na 2MoO 3, resulting in an irreversible phase transformation. Upon subsequent sodiation/desodiation cycles, however, a stable and reversible phase transformation between crystalline Mo and amorphous Na2MoO 3 phases has been revealed. In conclusion, our work provides an in-deepth understanding of the phase transformation pathways of α-MoO 3 nanobelts upon electrochemical sodiation/desodiation processes, with the hope of assistance in designing sodium-ion batteries with enhanced performance.« less

Template-assisted mineral formation via an amorphous liquid phase precursor route

NASA Astrophysics Data System (ADS)

Amos, Fairland F.

The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was implemented in calcium phosphate. Spherulitic crystals and films, seemingly formed from a molten state, were produced. These structures served as nucleating surfaces for the radial formation of calcium oxalate minerals. The composite calcium phosphate-calcium oxalate assemblies are similar to the core-shell structures found in certain kidney stones.

Experimental Study of the Microstructure and Micromechanical Properties of Laser Cladded Ni-based Amorphous Composite Coatings

NASA Astrophysics Data System (ADS)

Li, Ruifeng; Zheng, Qichi; Zhu, Yanyan; Li, Zhuguo; Feng, Kai; Liu, Chuan

2018-01-01

(Ni0.6Fe0.4)65B18Si10Nb4C3 amorphous composite coating was successfully fabricated on AISI 1045 steel substrate by using laser cladding process with coaxial powder feeding equipment. The microstructure and phase distribution of the coating were investigated by using x-ray diffraction, scanning electron microscopy and transmission electron microscope. The mechanical properties of the coating were examined by using microhardness testing and nanoindentation. The experimental results indicated that the volume fraction of amorphous phase increased with the decrease in laser cladding heat input, leading to an improvement of mean microhardness and nanohardness. NbC particles in a size ranging between 150 and 1650 nm were found embedding in the amorphous composite coatings in all situations. The presence of the NbC particles can contribute to an improvement of 96.7 HV in hardness on the basis of experimental results, while theoretical prediction suggests an improvement of 92.5 HV by using Orowan-Ashby equation.

Electron-irradiation-induced crystallization at metallic amorphous/silicon oxide interfaces caused by electronic excitation

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

Nagase, Takeshi, E-mail: t-nagase@uhvem.osaka-u.ac.jp; Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1, Yamada-Oka, Suita, Osaka 565-0871; Yamashita, Ryo

2016-04-28

Irradiation-induced crystallization of an amorphous phase was stimulated at a Pd-Si amorphous/silicon oxide (a(Pd-Si)/SiO{sub x}) interface at 298 K by electron irradiation at acceleration voltages ranging between 25 kV and 200 kV. Under irradiation, a Pd-Si amorphous phase was initially formed at the crystalline face-centered cubic palladium/silicon oxide (Pd/SiO{sub x}) interface, followed by the formation of a Pd{sub 2}Si intermetallic compound through irradiation-induced crystallization. The irradiation-induced crystallization can be considered to be stimulated not by defect introduction through the electron knock-on effects and electron-beam heating, but by the electronic excitation mechanism. The observed irradiation-induced structural change at the a(Pd-Si)/SiO{sub x} and Pd/SiO{sub x}more » interfaces indicates multiple structural modifications at the metal/silicon oxide interfaces through electronic excitation induced by the electron-beam processes.« less

Pressure-induced phase transformation, reversible amorphization, and anomalous visible light response in organolead bromide perovskite

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

Wang, Yonggang; Lu, Xujie; Yang, Wenge

Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH 3NH 3PbBr 3 (MAPbBr 3), under hydrostatic pressure up to 34 GPa at room temperature: Two phase transformations below 2 GPa (from Pm3¯m to Im3¯, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr 6 octahedra and destroying of long-rangemore » ordering of MA cations, respectively. The visible light response of MAPbBr 3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Lastly, our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.« less

Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

NASA Technical Reports Server (NTRS)

Dutta, Prabir K.

1995-01-01

Formation of zincophosphates from zinc and phosphate containing reverse micelles (water droplets in hexane) has been examined. The frameworks formed resemble that made by conventional hydrothermal synthesis. Dynamics of crystal growth are however quite different, and form the main focus of this study. In particular, the formation of zincophosphate with the sodalite framework was examined in detail. The intramicellar pH was found to have a strong influence on crystal growth. Crystals with a cubic morphology were formed directly from the micelles, without an apparent intermediate amorphous phase over a period of four days by a layer-bylayer growth at the intramicellar pH of 7.6. At a pH of 6.8, an amorphous precipitate rapidly sediments in hours. Sodalite was eventually formed from this settled phase via surface diffusion and reconstruction within four days. With a rotating cell, it was possible to minimize sedimentation and crystals were found to grow epitaxially from the spherical, amorphous particles. Intermediate pH's of 7.2 led to formation of aggregated sodalite crystals prior to settling, again without any indication of an intermediate amorphous phase. These diverse pathways were possible due to changes in intramicellar supersaturation conditions by minor changes in pH. In contrast, conventional syntheses in this pH range all proceeded by similar crystallization pathways through an amorphous gel. This study establishes that synthesis of microporous frameworks is not only possible in reverse micellar systems, but they also allow examination of possible crystallization pathways.

Properties of Amorphous Carbon Microspheres Synthesised by Palm Oil-CVD Method

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

Zobir, S. A. M.; Nano-SciTech Centre,; Zainal, Z.

2011-03-30

Amorphous carbon microspheres were synthesized using a dual-furnace chemical vapour deposition method at 800-1000 deg. C. Palm oil-based cooking oil (PO) and zinc nitrate solution was used as a carbon source and catalyst precursor, respectively with PO to zinc nitrate ratio of 30:20 (v/v) and a silicon wafer as the sample target. Regular microsphere shape of the amorphous carbons was obtained and a uniform microsphere structure improved as the carbonization temperature increased from 800 to 1000 deg. C. At 800 deg. C, no regular microspheres were formed but more uniform structure is observed at 900 deg. C. Generally the microspheresmore » size is uniform when the heating temperature was increased to 1000 deg. C, but the presence of mixed sizes can still be observed. X-ray diffraction patterns show the presence of oxide of carbon, ZnO phase together with Zn oxalate phase. Raman spectra show two broad peaks characteristic to amorphous carbon at 1344 and 1582 cm{sup -1} for the D and G bands, respectively. These bands become more prominent as the preparation temperature increased from 800 to 1000 deg. C. This is in agreement with the formation of amorphous carbon microspheres as shown by the FESEM study and other Zn-based phases as a result of the oxidation process of the palm oil as the carbon source and the zinc nitrate as the catalyst precursor, respectively.« less

Pressure-Induced Phase Transformation, Reversible Amorphization, and Anomalous Visible Light Response in Organolead Bromide Perovskite.

PubMed

Wang, Yonggang; Lü, Xujie; Yang, Wenge; Wen, Ting; Yang, Liuxiang; Ren, Xiangting; Wang, Lin; Lin, Zheshuai; Zhao, Yusheng

2015-09-02

Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH3NH3PbBr3 (MAPbBr3), under hydrostatic pressure up to 34 GPa at room temperature. Two phase transformations below 2 GPa (from Pm3̅m to Im3̅, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr6 octahedra and destroying of long-range ordering of MA cations, respectively. The visible light response of MAPbBr3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.

Pressure-induced phase transformation, reversible amorphization, and anomalous visible light response in organolead bromide perovskite

DOE PAGES

Wang, Yonggang; Lu, Xujie; Yang, Wenge; ...

2015-08-18

Hydrostatic pressure, as an alternative of chemical pressure to tune the crystal structure and physical properties, is a significant technique for novel function material design and fundamental research. In this article, we report the phase stability and visible light response of the organolead bromide perovskite, CH 3NH 3PbBr 3 (MAPbBr 3), under hydrostatic pressure up to 34 GPa at room temperature: Two phase transformations below 2 GPa (from Pm3¯m to Im3¯, then to Pnma) and a reversible amorphization starting from about 2 GPa were observed, which could be attributed to the tilting of PbBr 6 octahedra and destroying of long-rangemore » ordering of MA cations, respectively. The visible light response of MAPbBr 3 to pressure was studied by in situ photoluminescence, electric resistance, photocurrent measurements and first-principle simulations. The anomalous band gap evolution during compression with red-shift followed by blue-shift is explained by the competition between compression effect and pressure-induced amorphization. Along with the amorphization process accomplished around 25 GPa, the resistance increased by 5 orders of magnitude while the system still maintains its semiconductor characteristics and considerable response to the visible light irradiation. Lastly, our results not only show that hydrostatic pressure may provide an applicable tool for the organohalide perovskites based photovoltaic device functioning as switcher or controller, but also shed light on the exploration of more amorphous organometal composites as potential light absorber.« less

Pressure-induced amorphization of La{sub 1/3}TaO{sub 3}

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

Noked, O., E-mail: noked@bgu.ac.il; Physics Department, Ben-Gurion University, Beer Sheva 84105; Melchior, A.

2013-06-15

La{sub 1/3}TaO{sub 3}, an A-site cation deficient perovskite, has been studied under pressure by synchrotron X-ray powder diffraction and Raman spectroscopy. It undergoes irreversible pressure induced amorphization at P=18.5 GPa. An almost linear unit cell volume decrease vs. pressure is observed from ambient pressure up to the phase transition. The Raman spectroscopy also shows amorphization at the same pressure, with positive shifts of all modes as a function of pressure. The pressure dependence of the E{sub g} and A{sub 1g} Raman modes arising from the octahedral oxygen network is discussed. - Graphical abstract: La{sub 1/3}Tao{sub 3} exhibits linear pressure–volume relationmore » until irreversible pressure induced amorphization at 18.5 Gpa. - Highlights: • La{sub 1/3}TaO{sub 3} has been studied under pressure by synchrotron XRD and Raman spectroscopy. • La{sub 1/3}TaO{sub 3} undergoes irreversible pressure induced amorphization around 18.5 GPa. • The transition is manifested in both XRD and Raman measurements. • A linear P–V relation is observed from ambient pressure up to the phase transition.« less

Inverse Resistance Change Cr2Ge2Te6-Based PCRAM Enabling Ultralow-Energy Amorphization.

PubMed

Hatayama, Shogo; Sutou, Yuji; Shindo, Satoshi; Saito, Yuta; Song, Yun-Heub; Ando, Daisuke; Koike, Junichi

2018-01-24

Phase-change random access memory (PCRAM) has attracted much attention for next-generation nonvolatile memory that can replace flash memory and can be used for storage-class memory. Generally, PCRAM relies on the change in the electrical resistance of a phase-change material between high-resistance amorphous (reset) and low-resistance crystalline (set) states. Herein, we present an inverse resistance change PCRAM with Cr 2 Ge 2 Te 6 (CrGT) that shows a high-resistance crystalline reset state and a low-resistance amorphous set state. The inverse resistance change was found to be due to a drastic decrease in the carrier density upon crystallization, which causes a large increase in contact resistivity between CrGT and the electrode. The CrGT memory cell was demonstrated to show fast reversible resistance switching with a much lower operating energy for amorphization than a Ge 2 Sb 2 Te 5 memory cell. This low operating energy in CrGT should be due to a small programmed amorphous volume, which can be realized by a high-resistance crystalline matrix and a dominant contact resistance. Simultaneously, CrGT can break the trade-off relationship between the crystallization temperature and operating speed.

Thin-Film Phase Plates for Transmission Electron Microscopy Fabricated from Metallic Glasses.

PubMed

Dries, Manuel; Hettler, Simon; Schulze, Tina; Send, Winfried; Müller, Erich; Schneider, Reinhard; Gerthsen, Dagmar; Luo, Yuansu; Samwer, Konrad

2016-10-01

Thin-film phase plates (PPs) have become an interesting tool to enhance the contrast of weak-phase objects in transmission electron microscopy (TEM). The thin film usually consists of amorphous carbon, which suffers from quick degeneration under the intense electron-beam illumination. Recent investigations have focused on the search for alternative materials with an improved material stability. This work presents thin-film PPs fabricated from metallic glass alloys, which are characterized by a high electrical conductivity and an amorphous structure. Thin films of the zirconium-based alloy Zr65.0Al7.5Cu27.5 (ZAC) were fabricated and their phase-shifting properties were evaluated. The ZAC film was investigated by different TEM techniques, which reveal beneficial properties compared with amorphous carbon PPs. Particularly favorable is the small probability for inelastic plasmon scattering, which results from the combined effect of a moderate inelastic mean free path and a reduced film thickness due to a high mean inner potential. Small probability plasmon scattering improves contrast transfer at high spatial frequencies, which makes the ZAC alloy a promising material for PP fabrication.

First principles prediction of amorphous phases using evolutionary algorithms

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

Nahas, Suhas, E-mail: shsnhs@iitk.ac.in; Gaur, Anshu, E-mail: agaur@iitk.ac.in; Bhowmick, Somnath, E-mail: bsomnath@iitk.ac.in

2016-07-07

We discuss the efficacy of evolutionary method for the purpose of structural analysis of amorphous solids. At present, ab initio molecular dynamics (MD) based melt-quench technique is used and this deterministic approach has proven to be successful to study amorphous materials. We show that a stochastic approach motivated by Darwinian evolution can also be used to simulate amorphous structures. Applying this method, in conjunction with density functional theory based electronic, ionic and cell relaxation, we re-investigate two well known amorphous semiconductors, namely silicon and indium gallium zinc oxide. We find that characteristic structural parameters like average bond length and bondmore » angle are within ∼2% of those reported by ab initio MD calculations and experimental studies.« less

Transmission electron microscope analyses of alteration phases in martian meteorite MIL 090032

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Ishii, H. A.; Bradley, J. P.; Taylor, G. J.

2014-06-01

The nakhlite group of martian meteorites found in the Antarctic contain varying abundances of both martian and terrestrial secondary alteration phases. The aim of this study was to use transmission electron microscopy (TEM) to compare martian and terrestrial alteration embodied within a single nakhlite martian meteorite find - MIL 090032. Martian alteration veins in MIL 090032 are composed of poorly ordered Fe-smectite phyllosilicate. This poorly-ordered smectite appears to be equivalent to the nanocrystalline phyllosilicate/hydrated amorphous gel phase previously described in the martian alteration veins of other nakhlites. Chemical differences in this nanocrystalline phyllosilicate between different nakhlites imply localised alteration, which occurred close to the martian surface in MIL 090032. Both structurally and compositionally the nakhlite nanocrystalline phyllosilicate shows similarities to the amorphous/poorly ordered phase recently discovered in martian soil by the Mars Curiosity Rover at Rocknest, Gale Crater. Terrestrially derived alteration phases in MIL 090032 include jarosite and gypsum, amorphous silicates, and Fe-oxides and hydroxides. Similarities between the mineralogy and chemistry of the MIL 090032 terrestrial and martian alteration phases suggest the alteration conditions on Mars were similar to those in the Antarctic. At both sites a small amount of fluid at low temperatures infiltrated the rock and became acidic as a result of the conversion of Fe2+ to Fe3+ under oxidising conditions.

Morphological, structural, and spectral characteristics of amorphous iron sulfates

PubMed Central

Sklute, E. C.; Jensen, H. B.; Rogers, A. D.; Reeder, R. J.

2018-01-01

Current or past brine hydrologic activity on Mars may provide suitable conditions for the formation of amorphous ferric sulfates. Once formed, these phases would likely be stable under current Martian conditions, particularly at low- to mid-latitudes. Therefore, we consider amorphous iron sulfates (AIS) as possible components of Martian surface materials. Laboratory AIS were created through multiple synthesis routes and characterized with total X-ray scattering, thermogravimetric analysis, scanning electron microscopy, visible/near-infrared (VNIR), thermal infrared (TIR), and Mössbauer techniques. We synthesized amorphous ferric sulfates (Fe(III)2(SO4)3 · ~ 6–8H2O) from sulfate-saturated fluids via vacuum dehydration or exposure to low relative humidity (<11%). Amorphous ferrous sulfate (Fe(II)SO4 · ~1H2O) was synthesized via vacuum dehydration of melanterite. All AIS lack structural order beyond 11 Å. The short-range (<5 Å) structural characteristics of amorphous ferric sulfates resemble all crystalline reference compounds; structural characteristics for the amorphous ferrous sulfate are similar to but distinct from both rozenite and szomolnokite. VNIR and TIR spectral data for all AIS display broad, muted features consistent with structural disorder and are spectrally distinct from all crystalline sulfates considered for comparison. Mössbauer spectra are also distinct from crystalline phase spectra available for comparison. AIS should be distinguishable from crystalline sulfates based on the position of their Fe-related absorptions in the visible range and their spectral characteristics in the TIR. In the NIR, bands associated with hydration at ~1.4 and 1.9 μm are significantly broadened, which greatly reduces their detectability in soil mixtures. AIS may contribute to the amorphous fraction of soils measured by the Curiosity rover. PMID:29675340

Nature and origin of mineral coatings on volcanic rocks of the Black Mountain, Stonewall Mountain and Kane Springs wash volcanic centers, southern Nevada

NASA Technical Reports Server (NTRS)

Taranik, James V.; Noble, Donald C.; Hsu, Liang C.; Spatz, David M.

1987-01-01

Mineral coatings, including desert varnish on volcanic rocks of the semi-arid Basin and Range province are composted of amorphous, translucent films of Fe, Mn, Si, and Al rich compounds. Coatings are chiefly thin films that impregnate intergranularly to depths of about 0.1 to 0.3 mm, rarely deeper. Sixteen coating sections and subsurface interiors were probed by SEM; 20 samples were scanned by infrated spectrometry; 10 samples were scanned for visible-near IR spectra; inductin coupling plasma analyses were collected on 34 samples; 2 desert varnish surgaces were investigated by optical density slice imagery; a few XRD analyses were conducted in addition to the 50 reported in the last period; thin section observation continued; and imagery processing focused on classification techniques. In late May, approximately 10 field days were spent at the Stonewall and Black Mountain study sited conducting more detailed mapping and observation base on imagery results and collecting spectra with the Collins Field Spectrometer. Approximately 100 spectral analyses were collected and are currently being processed.

NMR Relaxometry to Characterize the Drug Structural Phase in a Porous Construct.

PubMed

Thrane, Linn W; Berglund, Emily A; Wilking, James N; Vodak, David; Seymour, Joseph D

2018-06-14

Nuclear magnetic resonance (NMR) frequency spectra and T 2 relaxation time measurements, using a high-power radio frequency probe, are shown to characterize the presence of an amorphous drug in a porous silica construct. The results indicate the ability of non-solid-state NMR methods to characterize crystalline and amorphous solid structural phases in drugs. Two-dimensional T 1 - T 2 magnetic relaxation time correlation experiments are shown to monitor the impact of relative humidity on the drug in a porous silica tablet.

Electrical and structural characterization of IZO (indium oxide-zinc oxide) thin films for device applications

NASA Astrophysics Data System (ADS)

Yaglioglu, Burag

Materials for oxide-based transparent electronics have been recently reported in the literature. These materials include various amorphous and crystalline compounds based on multi-component oxides and many of them offer useful combinations of transparency, controllable carrier concentrations, and reasonable n-carrier mobility. In this thesis, the properties of amorphous and crystalline In2O3-10wt%ZnO, IZO, thin films were investigated for their potential use in oxide electronics. The room temperature deposition of this material using DC magnetron sputtering results in the formation of amorphous films. Annealing amorphous IZO films at 500°C in air produces a previously unknown crystalline compound. Using electron diffraction experiments, it is reported that the crystal structure of this compound is based on the high-pressure rhombohedral phase of In2O3. Electrical properties of different phases of IZO were explored and it was concluded that amorphous films offer most promising characteristics for device applications. Therefore, thin film transistors (TFT) were fabricated based on amorphous IZO films where both the channel and metallization layers were deposited from the same target. The carrier densities in the channel and source-drain layers were adjusted by changing the oxygen content in the sputter chamber during deposition. The resulting transistors operate as depletion mode n-channel field effect devices with high saturation mobilities.

Absence of pressure-induced amorphization in LiKSO4.

PubMed

Machon, D; Pinheiro, C B; Bouvier, P; Dmitriev, V P; Crichton, W A

2010-08-11

Angle-resolved synchrotron radiation diffraction was used to investigate lithium potassium sulfate (LiKSO(4)) crystals under high pressure. We confirm that the title compound undergoes three phase transitions, α →β, β → γ and γ →δ, observed at around 0.8 GPa, 4.0 GPa and 7.0 GPa, respectively. Two competitive structures are proposed for the β-phase after powder diffraction data Rietveld refinements: an orthorhombic (space group Cmc 2(1)) or a monoclinic (space group Cc) structure. These structures correspond to the models of the low temperature phases. The γ-phase is indexed by a monoclinic structure. Finally, the δ-phase is found to be highly disordered. No evidence of any pressure-induced amorphous phase was observed up to 24 GPa, even under imposed highly non-hydrostatic conditions, contrary to previous propositions.

Modeling and impacts of the latent heat of phase change and specific heat for phase change materials

NASA Astrophysics Data System (ADS)

Scoggin, J.; Khan, R. S.; Silva, H.; Gokirmak, A.

2018-05-01

We model the latent heats of crystallization and fusion in phase change materials with a unified latent heat of phase change, ensuring energy conservation by coupling the heat of phase change with amorphous and crystalline specific heats. We demonstrate the model with 2-D finite element simulations of Ge2Sb2Te5 and find that the heat of phase change increases local temperature up to 180 K in 300 nm × 300 nm structures during crystallization, significantly impacting grain distributions. We also show in electrothermal simulations of 45 nm confined and 10 nm mushroom cells that the higher amorphous specific heat predicted by this model increases nucleation probability at the end of reset operations. These nuclei can decrease set time, leading to variability, as demonstrated for the mushroom cell.

Carbon-doped Ge2Sb2Te5 phase change material: A candidate for high-density phase change memory application

NASA Astrophysics Data System (ADS)

Zhou, Xilin; Wu, Liangcai; Song, Zhitang; Rao, Feng; Zhu, Min; Peng, Cheng; Yao, Dongning; Song, Sannian; Liu, Bo; Feng, Songlin

2012-10-01

Carbon-doped Ge2Sb2Te5 material is proposed for high-density phase-change memories. The carbon doping effects on electrical and structural properties of Ge2Sb2Te5 are studied by in situ resistance and x-ray diffraction measurements as well as optical spectroscopy. C atoms are found to significantly enhance the thermal stability of amorphous Ge2Sb2Te5 by increasing the degree of disorder of the amorphous phase. The reversible electrical switching capability of the phase-change memory cells is improved in terms of power consumption with carbon addition. The endurance of ˜2.1 × 104 cycles suggests that C-doped Ge2Sb2Te5 film will be a potential phase-change material for high-density storage application.

Local Crystalline Structure in an Amorphous Protein Dense Phase

PubMed Central

Greene, Daniel G.; Modla, Shannon; Wagner, Norman J.; Sandler, Stanley I.; Lenhoff, Abraham M.

2015-01-01

Proteins exhibit a variety of dense phases ranging from gels, aggregates, and precipitates to crystalline phases and dense liquids. Although the structure of the crystalline phase is known in atomistic detail, little attention has been paid to noncrystalline protein dense phases, and in many cases the structures of these phases are assumed to be fully amorphous. In this work, we used small-angle neutron scattering, electron microscopy, and electron tomography to measure the structure of ovalbumin precipitate particles salted out with ammonium sulfate. We found that the ovalbumin phase-separates into core-shell particles with a core radius of ∼2 μm and shell thickness of ∼0.5 μm. Within this shell region, nanostructures comprised of crystallites of ovalbumin self-assemble into a well-defined bicontinuous network with branches ∼12 nm thick. These results demonstrate that the protein gel is comprised in part of nanocrystalline protein. PMID:26488663

Intergranular diffusion and embrittlement of a Ni-16Mo-7Cr alloy in Te vapor environment

NASA Astrophysics Data System (ADS)

Cheng, Hongwei; Li, Zhijun; Leng, Bin; Zhang, Wenzhu; Han, Fenfen; Jia, Yanyan; Zhou, Xingtai

2015-12-01

Nickel and some nickel-base alloys are extremely sensitive to intergranular embrittlement and tellurium (Te) enhanced cracking, which should be concerned during their serving in molten salt reactors. Here, a systematic study about the effects of its temperature on the reaction products at its surface, the intergranular diffusion of Te in its body and its embrittlement for a Ni-16Mo-7Cr alloy contacting Te is reported. For exposed to Te vapor at high temperature (823-1073 K), the reaction products formed on the surface of the alloy were Ni3Te2, CrTe, and MoTe2, and the most serious embrittlement was observed at 1073 K. The kinetic measurement in terms of Te penetration depth in the alloy samples gives an activation energy of 204 kJ/mol. Electron probe microanalysis confirmed the local enrichment of Te at grain boundaries. And clearly, the embrittlement was results from the intergranular diffusion and segregation of element Te.

Modeling of grain boundary stresses in Alloy 600

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

Kozaczek, K.J.; Sinharoy, A.; Ruud, C.O.

1995-04-01

Corrosive environments combined with high stress levels and susceptible microstructures can cause intergranular stress corrosion cracking (IGSCC) of Alloy 600 components on both primary and secondary sides of pressurized water reactors. One factor affecting the IGSCC is intergranular carbide precipitation controlled by heat treatment of Alloy 600. This study is concerned with analysis of elastic stress fields in vicinity of M{sub 7}C{sub 3} and M{sub 23}C{sub 6} carbides precipitated in the matrix and at a grain boundary triple point. The local stress concentration which can lead to IGSCC initiation was studied using a two-dimensional finite element model. The intergranular precipitatesmore » are more effective stress raisers than the intragranular precipitates. The combination of the elastic property mismatch and the precipitate shape can result in a local stress field substantially different than the macroscopic stress. The maximum local stresses in the vicinity of the intergranular precipitate were almost twice as high as the applied stress.« less

The application of in situ analytical transmission electron microscopy to the study of preferential intergranular oxidation in Alloy 600.

PubMed

Burke, M G; Bertali, G; Prestat, E; Scenini, F; Haigh, S J

2017-05-01

In situ analytical transmission electron microscopy (TEM) can provide a unique perspective on dynamic reactions in a variety of environments, including liquids and gases. In this study, in situ analytical TEM techniques have been applied to examine the localised oxidation reactions that occur in a Ni-Cr-Fe alloy, Alloy 600, using a gas environmental cell at elevated temperatures. The initial stages of preferential intergranular oxidation, shown to be an important precursor phenomenon for intergranular stress corrosion cracking in pressurized water reactors (PWRs), have been successfully identified using the in situ approach. Furthermore, the detailed observations correspond to the ex situ results obtained from bulk specimens tested in hydrogenated steam and in high temperature PWR primary water. The excellent agreement between the in situ and ex situ oxidation studies demonstrates that this approach can be used to investigate the initial stages of preferential intergranular oxidation relevant to nuclear power systems. Copyright © 2016 Elsevier B.V. All rights reserved.

Amorphous calcium carbonate: A precursor phase for aragonite in shell disease of the pearl oyster.

PubMed

Huang, Jingliang; Liu, Chuang; Xie, Liping; Zhang, Rongqing

2018-02-26

Amorphous calcium carbonate (ACC) has long been shown to act as an important constituent or precursor phase for crystalline material in mollusks. However, the presence and the role of ACC in bivalve shell formation are not fully studied. In this study, we found that brown deposits containing heterogeneous calcium carbonates were precipitated when a shell disease occurred in the pearl oyster Pinctada fucata. Calcein-staining of the brown deposits indicated that numerous amorphous calcium deposits were present, which was further confirmed by Fourier-transform infrared spectroscopy (FTIR), Raman spectrum and X-ray difraction (XRD) analyses. So we speculate that ACC plays an important role in rapid calcium carbonate precipitation during shell repair process in diseased oysters. Copyright © 2018 Elsevier Inc. All rights reserved.

Reversible pressure pre-amorphization of a piezochromic metal-organic framework.

PubMed

Andrzejewski, M; Casati, N; Katrusiak, A

2017-11-07

The piezochromic metal-organic framework Co 2 (Bdc) 2 Dabco·4DMF·H 2 O (Bdc denotes 1,4-benzenedicarboxylate, Dabco - 1,4-diazabicyclo[2.2.2]octane, and DMF - dimethylformamide) under ambient conditions is tetragonal (phase α) and at about 1.9 GPa undergoes a strong pressure-induced shortening of translational correlations in the sample. A broad gradual pre-amorphization process starting at about 0.7 GPa reduces the tetragonal symmetry and is described as phase β. The pre-amorphization mechanism involves several competing distortions of the Bdc linkers and Co(ii)-coordination schemes. These in turn, affect the crystal field around the cations and their optical absorption. The compression strongly affects the VIS absorption of this piezochromic compound visibly changing its colour from blue to red.

Extensively Reversible Thermal Transformations of a Bistable, Fluorescence-Switchable Molecular Solid: Entry into Functional Molecular Phase-Change Materials.

PubMed

Srujana, P; Radhakrishnan, T P

2015-06-15

Functional phase-change materials (PCMs) are conspicuously absent among molecular materials in which the various attributes of inorganic solids have been realized. While organic PCMs are primarily limited to thermal storage systems, the amorphous-crystalline transformation of materials like Ge-Sb-Te find use in advanced applications such as information storage. Reversible amorphous-crystalline transformations in molecular solids require a subtle balance between robust supramolecular assembly and flexible structural elements. We report novel diaminodicyanoquinodimethanes that achieve this transformation by interlinked helical assemblies coupled with conformationally flexible alkoxyalkyl chains. They exhibit highly reversible thermal transformations between bistable (crystalline/amorphous) forms, along with a prominent switching of the fluorescence emission energy and intensity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

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

McMillan, Paul F.; Gryko, Jan; Bull, Craig

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr{sub 2}) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300{sup o}C. Syntheses at higher temperatures gave rise tomore » microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.« less

First-principles study of amorphous Ga4Sb6Te3 phase-change alloys

NASA Astrophysics Data System (ADS)

Bouzid, Assil; Gabardi, Silvia; Massobrio, Carlo; Boero, Mauro; Bernasconi, Marco

2015-05-01

First-principles molecular dynamics simulations within the density functional theory framework were performed to generate amorphous models of the Ga4Sb6Te3 phase change alloy by quenching from the melt. We find that Ga-Sb and Ga-Te are the most abundant bonds with only a minor amount of Sb-Te bonds participating to the alloy network. Ga and four-coordinated Sb atoms present a tetrahedral-like geometry, whereas three-coordinated Sb atoms are in a pyramidal configuration. The tetrahedral-like geometries are similar to those of the crystalline phase of the two binary compounds GaTe and GaSb. A sizable fraction of Sb-Sb bonds is also present, indicating a partial nanoscale segregation of Sb. Despite the fact that the composition Ga4Sb6Te3 lies on the pseudobinary Ga Sb -Sb2Te3 tie line, the amorphous network can be seen as a mixture of the two binary compounds GaTe and GaSb with intertwined elemental Sb.

Nanoscale Transforming Mineral Phases in Fresh Nacre

DOE PAGES

DeVol, Ross T.; Sun, Chang-Yu; Marcus, Matthew A.; ...

2015-09-24

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO 3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropodmore » shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO 3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.« less

Crystallization kinetics of the phase change material GeSb 6Te measured with dynamic transmission electron microscopy

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

Winseck, M. M.; Cheng, H. -Y.; Campbell, G. H.

2016-03-30

GeSb 6Te is a chalcogenide-based phase change material that has shown great ptoential for use in solid-state memory devices. The crystallization kinetics of amorphous thin films of GeSb 6Te during laser crystallization were followed with dynamic transmission electron microscopy, a photo-emission electron microscopy technique with nanosecond-scale time resolution. Nine-frame movies of crystal growth were taken during laser crystallization. The nucleation rate is observed to be very low and the growth rates are very high, up to 10.8 m s –1 for amorphous as-deposited films and significantly higher for an amorphous film subject to sub-threshold laser annealing before crystallization. The measuredmore » growth rates exceed any directly measured growth rate of a phase change material. Here, the crystallization is reminiscent of explosive crystallization of elemental semiconductors both in the magnitude of the growth rate and in the resulting crystalline microstructures.« less

Synthesis and Characterization of Zr-BASED Amorphous and Crystalline Composite Coating on Ti Substrate by Laser Cladding

NASA Astrophysics Data System (ADS)

Tang, D. M.; Zhang, D. C.; Peng, W.; Luo, Z. C.; Wu, X. Q.; Wang, Y. M.; Lin, J. G.

2014-02-01

A thin strip of a Zr-based alloy with a composition of Zr60Cu25Fe5Al10 (in atom percent) was used as a raw material, and the composite coatings containing Zr-based amorphous phase and crystallites on Ti substrate were fabricated by a one-step laser cladding method without protection. The microstructure, phase constitution, microhardness and wear properties of the coatings were investigated. The results indicate that the microstructure of the coatings is strongly dependent on the laser scanning speed under the conditions of the laser power of 1300 W and laser beam diameter of 6 mm, and the composite coating mainly containing amorphous phase with a small amount of the crystallites can be obtained at the laser scanning speed of 10 mm/s. The composite coating exhibits much higher microhardness than the pure Ti substrate, and thus it behaves superior wear resistance in comparison with the substrate.

Phase analysis of ZrO2-SiO2 systems synthesized through Ball milling mechanical activations

NASA Astrophysics Data System (ADS)

Nurlaila, Rizka; Musyarofah, Muwwaqor, Nibras Fuadi; Triwikantoro, Kuswoyo, Anton; Pratapa, Suminar

2017-01-01

Zircon powders have been produced from raw materials of amorphous zirconia and amorphous silica powders obtained from natural zircon sand of Kalimantan Tengah, Indonesia. Synthesis process was started with the extraction of zircon powder to produce sodium silicate solution and pure zircon powder. The amorphous zirconia and silica powders were prepared by alkali fusion and co-precipitation techniques. The powders were mixed using a planetary ball mill, followed by a calcination of various holding time of 3, 10, and 15 h. Phase characterization was done using X-Ray Diffraction (XRD) technique and analysis of the diffraction data was carried out using Rietica and MAUD software. The identified phases after the calcination were zircon, tetragonal zirconia, and cristobalite. The highest zircon content was obtained in the sample calcinated for15 hours - reaching 99.66 %wt. Crystallite size analysis revealed that the samples calcinated for 3, 10, and 15 h exhibited zircon crystal size of 176 (1) nm, 191 (1) nm and 233 (1) nm respectively.

Biogenic Fish-gut Calcium Carbonate is a Stable Amorphous Phase in the Gilt-head Seabream, Sparus aurata

PubMed Central

Foran, Elizabeth; Weiner, Steve; Fine, Maoz

2013-01-01

The main source of calcium carbonate (CaCO3) in the ocean comes from the shells of calcifying planktonic organisms, but substantial amounts of CaCO3 are also produced in fish intestines. The precipitation of CaCO3 assists fish in intestinal water absorption and aids in whole body Ca2+ homeostasis. Here we report that the product formed in the intestinal lumen of the gilt-head seabream, Sparus aurata, is an amorphous calcium carbonate (ACC) phase. With FTIR spectroscopy and SEM imaging, our study shows that the fish-derived carbonates from S. aurata are maintained as a stable amorphous phase throughout the intestinal tract. Moreover, intestinal deposits contained up to 54 mol% Mg2+, the highest concentration yet reported in biogenic ACC. Mg is most likely responsible for stabilizing this inherently unstable mineral. The fish carbonates also displayed initial rapid dissolution when exposed to seawater, exhibiting a significant increase in carbonate concentration. PMID:23609008

Polyamorphism in tetrahedral substances: Similarities between silicon and ice

NASA Astrophysics Data System (ADS)

Garcez, K. M. S.; Antonelli, A.

2015-07-01

Tetrahedral substances, such as silicon, water, germanium, and silica, share various unusual phase behaviors. Among them, the so-called polyamorphism, i.e., the existence of more than one amorphous form, has been intensively investigated in the last three decades. In this work, we study the metastable relations between amorphous states of silicon in a wide range of pressures, using Monte Carlo simulations. Our results indicate that the two amorphous forms of silicon at high pressures, the high density amorphous (HDA) and the very high density amorphous (VHDA), can be decompressed from high pressure (˜20 GPa) down to the tensile regime, where both convert into the same low density amorphous. Such behavior is also observed in ice. While at high pressure (˜20 GPa), HDA is less stable than VHDA, at the pressure of 10 GPa both forms exhibit similar stability. On the other hand, at much lower pressure (˜5 GPa), HDA and VHDA are no longer the most stable forms, and, upon isobaric annealing, an even less dense form of amorphous silicon emerges, the expanded high density amorphous, again in close similarity to what occurs in ice.

High pressure polymorphs and amorphization of upconversion host material NaY(WO 4) 2

DOE PAGES

Hong, Fang; Yue, Binbin; Cheng, Zhenxiang; ...

2016-07-29

The pressure effect on the structural change of upconversion host material NaY(WO 4) 2 was studied in this paper by using in-situ synchrotron X-ray diffraction. A transition from the initial scheelite phase to the M-fergusonite phase occurs near 10 GPa, and another phase transition is found near 27.5 GPa, which could be an isostructural transition without symmetry change. The sample becomes amorphous when the pressure is fully released from high pressure. Finally, this work demonstrates the possibility of synthesizing various polymorph structures for non-linear optical applications with a high pressure, chemical doping, or strained thin-film nanostructure process.

An IR investigation of solid amorphous ethanol - Spectra, properties, and phase changes

NASA Astrophysics Data System (ADS)

Hudson, Reggie L.

2017-12-01

Mid- and far-infrared spectra of condensed ethanol (CH3CH2OH) at 10-160 K are presented, with a special focus on amorphous ethanol, the form of greatest astrochemical interest, and with special attention given to changes at 155-160 K. Infrared spectra of amorphous and crystalline forms are shown. The refractive index at 670 nm of amorphous ethanol at 16 K is reported, along with three IR band strengths and a density. A comparison is made to recent work on the isoelectronic compound ethanethiol (CH3CH2SH), and several astrochemical applications are suggested for future study.

An IR Investigation of Solid Amorphous Ethanol-Spectra, Properties, and Phase Changes

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.

2017-01-01

Mid- and far-infrared spectra of condensed ethanol (CH3CH2OH) at 10-160 K are presented, with a special focus on amorphous ethanol, the form of greatest astrochemical interest, and with special attention given to changes at 155-160 K. Infrared spectra of amorphous and crystalline forms are shown. The refractive index at 670 nm of amorphous ethanol at 16 K is reported, along with three IR band strengths and a density. A comparison is made to recent work on the isoelectronic compound ethanethiol (CH3CH2SH), and several astrochemical applications are suggested for future study.

Peculiarities of Vibration Characteristics of Amorphous Ices

NASA Astrophysics Data System (ADS)

Gets, Kirill V.; Subbotin, Oleg S.; Belosludov, Vladimir R.

2012-03-01

Dynamic properties of low (LDA), high (HDA) and very high (VHDA) density amorphous ices were investigated within the approach based on Lattice Dynamics simulations. In this approach, we assume that the short-range molecular order mainly determines the dynamic and thermodynamic properties of amorphous ices. Simulation cell of 512 water molecules with periodical boundary conditions and disordering allows us to study dynamical properties and dispersion curves in the Brillouin zone of pseudo-crystal. Existence of collective phenomena in amorphous ices which is usual for crystals but anomalous for disordered phase was confirmed in our simulations. Molecule amplitudes of delocalized (collective) as well as localized vibrations have been considered.

Atomic mixing induced by swift heavy ion irradiation of Fe/Zr multilayers

NASA Astrophysics Data System (ADS)

Jaouen, C.; Michel, A.; Pacaud, J.; Dufour, C.; Bauer, Ph.; Gervais, B.

1999-01-01

The mechanism of ion induced mixing and phase change was studied for Fe/Zr multilayers, and specifically for the case of swift heavy ions giving rise to a very large electronic excitation of the target. The multilayers had a modulation of 7.6 nm and an overall composition Fe 69Zr 31. The Zr layers were amorphous whereas the Fe ones were crystalline (bcc) with a very strong (1 1 0) texture in the growth direction. The phase transformation and the composition changes were analysed using the structural and magnetic properties of the Fe component by means of a detailed analysis of the X-ray diffraction profiles and with the aid of backscattering Mössbauer spectroscopy. A complete mixing was observed at a fluence of 10 13 U/cm 2. Both phenomena, the dose dependence of the ion beam mixed amorphous non-magnetic phase and the quantitative evolution of the crystalline iron layer thickness, suggest that mixing occurs in a two-stage process. At an initial stage, an anisotropic diffusion of iron atoms in the amorphous zirconium layers takes place along the interface, while subsequent ion bombardment leads to a generalised transformation through the whole of the Fe layer. Finally, the implications of these observations are discussed in comparison to the plastic deformation phenomena reported for amorphous alloys.

Current status of amorphous formulation and other special dosage forms as formulations for early clinical phases.

PubMed

Kawakami, Kohsaku

2009-09-01

Although most chemists in the pharmaceutical industry have a good understanding on favorable physicochemical properties for drug candidates, formulators must still deal with many challenging candidates. On the other hand, formulators are not allowed to spend much time on formulation development for early phases of the clinical studies. Thus, it is basically difficult to apply special dosage form technologies to the candidates for the first-in-human formulations. Despite the availability of numerous reviews on oral special dosage forms, information on their applicability as the early phase formulation has been limited. This article describes quick review on the oral special dosage forms that may be applied to the early clinical formulations, followed by discussion focused on the amorphous formulations, which still has relatively many issues to be proved for the general use. The major problems that inhibit the use of the amorphous formulation are difficulty in the manufacturing and the poor chemical/physical stability. Notably, the poor physical stability can be critical, because of not the poor stability itself but the difficulty in the timely evaluation in the preclinical developmental timeframes. Research directions of the amorphous formulations are suggested to utilize this promising technology without disturbing the preclinical developmental timelines.

Microstructural Modeling of Dynamic Intergranular and Transgranular Fracture Modes in Zircaloys

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

Mohammed, I.; Zikry, M.A.; Ziaei, S.

2017-04-01

In this time period, we have continued to focus on (i) refining the thermo-mechanical fracture model for zirconium (Zr) alloys subjected to large deformations and high temperatures that accounts for the cracking of ZrH and ZrH2 hydrides, (ii) formulating a framework to account intergranular fracture due to iodine diffusion and pit formation in grain-boundaries (GBs). Our future objectives are focused on extending to a combined population of ZrH and ZrH2 populations and understanding how thermo-mechanical behavior affects hydride reorientation and cracking. We will also refine the intergranular failure mechanisms for grain boundaries with pits.

Method of forming semiconducting amorphous silicon films from the thermal decomposition of fluorohydridodisilanes

DOEpatents

Sharp, Kenneth G.; D'Errico, John J.

1988-01-01

The invention relates to a method of forming amorphous, photoconductive, and semiconductive silicon films on a substrate by the vapor phase thermal decomposition of a fluorohydridodisilane or a mixture of fluorohydridodisilanes. The invention is useful for the protection of surfaces including electronic devices.

Influence of Surrounding Dielectrics on the Data Retention Time of Doped Sb2Te Phase Change Material

NASA Astrophysics Data System (ADS)

Jedema, Friso; in `t Zandt, Micha; Wolters, Rob; Gravesteijn, Dirk

2011-02-01

The crystallization properties of as-deposited and laser written amorphous marks of doped Sb2Te phase change material are found to be only dependent on the top dielectric layer. A ZnS:SiO2 top dielectric layer yields a higher crystallization temperature and a larger crystal growth activation energy as compared to a SiO2 top dielectric layer, leading to superior data retention times at ambient temperatures. The observed correlation between the larger crystallization temperatures and larger crystal growth activation energies indicates that the viscosity of the phase change material in the amorphous state is dependent on the interfacial energy between the phase change material and the top dielectric layer.

In-situ characterization of the optical and electronic properties in GeTe and GaSb thin films

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

Velea, A.; Popescu, M.; Galca, A. C., E-mail: ac-galca@infim.ro

2015-10-07

GeTe and GaSb thin films obtained by pulsed laser deposition were investigated by spectroscopic ellipsometry at controlled temperatures. The GeTe films were fully amorphous, while the GaSb films were partially crystalized in the as-deposited state. The Tauc-Lorentz model was employed to fit the experimental data. From the temperature study of the optical constants, it was observed the crystallization in the 150–160 °C range of GeTe amorphous films and between 230 and 240 °C of GaSb amorphous phase. A second transition in the resonance energy and the broadening parameter of the Lorentz oscillator was observed due to the crystallization of Sb after 250 °C.more » The temperatures of 85 °C and 130 °C are noticed as the start of the relaxation of the amorphous GeTe phase and as-deposited GaSb. The peaks of the imaginary part of the dielectric function red shifted after the phase change, while the variation with temperature of the crystalline phase follows the Varshni law. The electron-phonon coupling constants are 2.88 and 1.64 for c-GeTe and c-GaSb, respectively. An optical contrast up to 60% was obtained for GeTe films and a maximum value of 7.5% is revealed in the case GaSb, which is altered by the partial crystallinity of the as-deposited films.« less

Amorphization of Serpentine at High Pressure and High Temperature

PubMed

Irifune; Kuroda; Funamori; Uchida; Yagi; Inoue; Miyajima

1996-06-07

Pressure-induced amorphization of serpentine was observed at temperatures of 200° to 300°C and pressures of 14 to 27 gigapascals with a combination of a multianvil apparatus and synchrotron radiation. High-pressure phases then crystallized rapidly when the temperature was increased to 400°C. These results suggest that amorphization of serpentine is an unlikely mechanism for generating deep-focus earthquakes, as the temperatures of subducting slabs are significantly higher than those of the rapid crystallization regime.

Low temperature production of large-grain polycrystalline semiconductors

DOEpatents

Naseem, Hameed A [Fayetteville, AR; Albarghouti, Marwan [Loudonville, NY

2007-04-10

An oxide or nitride layer is provided on an amorphous semiconductor layer prior to performing metal-induced crystallization of the semiconductor layer. The oxide or nitride layer facilitates conversion of the amorphous material into large grain polycrystalline material. Hence, a native silicon dioxide layer provided on hydrogenated amorphous silicon (a-Si:H), followed by deposited Al permits induced crystallization at temperatures far below the solid phase crystallization temperature of a-Si. Solar cells and thin film transistors can be prepared using this method.

Effect of Microstructure and Alloy Chemistry on Hydrogen Embrittlement of Precipitation-Hardened Ni-Based Alloys

NASA Astrophysics Data System (ADS)

Obasi, G. C.; Zhang, Z.; Sampath, D.; Morana, Roberto; Akid, R.; Preuss, M.

2018-04-01

The sensitivity to hydrogen embrittlement (HE) has been studied in respect of precipitation size distributions in two nickel-based superalloys: Alloy 718 (UNS N07718) and Alloy 945X (UNS N09946). Quantitative microstructure analysis was carried out by the combination of scanning and transmission electron microscopy and energy dispersive x-ray spectroscopy (EDS). While Alloy 718 is mainly strengthened by γ″, and therefore readily forms intergranular δ phase, Alloy 945X has been designed to avoid δ formation by reducing Nb levels providing high strength through a combination of γ' and γ″. Slow strain rate tensile tests were carried out for different microstructural conditions in air and after cathodic hydrogen (H) charging. HE sensitivity was determined based on loss of elongation due to the H uptake in comparison to elongation to failure in air. Results showed that both alloys exhibited an elevated sensitivity to HE. Fracture surfaces of the H precharged material showed quasi-cleavage and transgranular cracks in the H-affected region, while ductile failure was observed toward the center of the sample. The crack origins observed on the H precharged samples exhibited quasi-cleavage with slip traces at high magnification. The sensitivity is slightly reduced for Alloy 718, by coarsening γ″ and reducing the overall strength of the alloy. However, on further coarsening of γ″, which promotes continuous decoration of grain boundaries with δ phase, the embrittlement index rose again indicating a change of hydrogen embrittlement mechanism from hydrogen-enhanced local plasticity (HELP) to hydrogen-enhanced decohesion embrittlement (HEDE). In contrast, Alloy 945X displayed a strong correlation between strength, based on precipitation size and embrittlement index, due to the absence of any significant formation of δ phase for the investigated microstructures. For the given test parameters, Alloy 945X did not display any reduced sensitivity to HE compared with Alloy 718 when considering high-strength conditions despite the absence of intergranular δ phase.

Search for the First-Order Liquid-to-Liquid Phase Transition in Low-Temperature Confined Water by Neutron Scattering

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

Chen, Sow-Hsin; Wang, Zhe; Kolesnikov, Alexander I

2013-01-01

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaricmore » temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the alpha-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.« less

Search for the first-order liquid-to-liquid phase transition in low-temperature confined water by neutron scattering

NASA Astrophysics Data System (ADS)

Chen, Sow-Hsin; Wang, Zhe; Kolesnikov, Alexander I.; Zhang, Yang; Liu, Kao-Hsiang

2013-02-01

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaric temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the α-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.

Appling grain boundary engineering to Alloy 690 tube for enhancing intergranular corrosion resistance

NASA Astrophysics Data System (ADS)

Xia, Shuang; Li, Hui; Liu, Ting Guang; Zhou, Bang Xin

2011-09-01

The feasibility of applying the grain boundary engineering (GBE) processing to Alloy 690 tube manufacturing for improving the intergranular corrosion resistance was studied. Through small amount of deformation by cold drawing using a draw-bench on a production line and subsequent short time annealing at high temperature, the proportion of low Σ coincidence site lattice (CSL) grain boundaries of the Alloy 690 tube can be enhanced to about 75% which mainly were of Σ3 n ( n = 1, 2, 3, …) type. In this case, the grain boundary network (GBN) was featured by the formation of highly twinned large size grain-clusters produced by multiple twinning during recrystallization. All of the grains inside this kind of cluster had Σ3 n mutual misorientations, and hence all the boundaries inside the cluster were of Σ3 n type and formed many interconnected Σ3 n type triple junctions. The weight losses due to grain dropping during intergranular corrosion for the samples with the modified GBN were much less than that with conventional microstructure. Based on the characterization by scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) technique, it was shown that the highly twinned large size grain-cluster microstructure played a key role in enhancing the intergranular corrosion resistance: (1) the large grain-cluster can arrest the penetration of intergranular corrosion; (2) the large grain-cluster can protect the underlying microstructure.

Characterization of adsorption sites on aggregate soil samples using synchrotron X-ray computerized microtomography.

PubMed

Altman, Susan J; Rivers, Mark L; Reno, Marissa D; Cygan, Randall T; McLain, Angela A

2005-04-15

Synchrotron-source X-ray computerized microtomography (CMT) was used to evaluate the adsorptive properties of aggregate soil samples. A linear relationship between measured mean mass attenuation coefficient (sigma) and mass fraction iron was generated by imaging mineral standards with known iron contents. On the basis of reported stoichiometries of the clay minerals and identifications of iron oxyhydroxides (1), we calculated the mass fraction iron and iron oxyhydroxide in the intergranular material. The mass fractions of iron were estimated to range from 0.17 to 0.22 for measurements made at 18 keV and from 0.18 to 0.21 for measurements made at 26 keV. One aggregate sample also contained regions within the intergranular material with mass fraction iron ranging from 0.29 to 0.31 and from 0.33 to 0.36 for the 18 and 26 keV measurements, respectively. The mass fraction iron oxyhydroxide ranged from 0.18 to 0.35 for the low-iron intergranular material and from 0.40 to 0.59 for the high-iron intergranular material. Using absorption edge difference imaging with CMT, we visualized cesium on the intergranular material, presumably because of adsorption and possible exchange reactions. By characterizing the mass fraction iron, the mass fraction iron oxyhydroxide, and the adsorptive capacity of these soil mineral aggregates, we provide information useful for conceptualization, development, and parametrization of transport models.

Magnetomechanical coupling in thermal amorphous solids

NASA Astrophysics Data System (ADS)

Hentschel, H. George E.; Ilyin, Valery; Mondal, Chandana; Procaccia, Itamar

2018-05-01

Standard approaches to magnetomechanical interactions in thermal magnetic crystalline solids involve Landau functionals in which the lattice anisotropy and the resulting magnetization easy axes are taken explicitly into account. In glassy systems one needs to develop a theory in which the amorphous structure precludes the existence of an easy axis, and in which the constituent particles are free to respond to their local amorphous surroundings and the resulting forces. We present a theory of all the mixed responses of an amorphous solid to mechanical strains and magnetic fields. Atomistic models are proposed in which we test the predictions of magnetostriction for both bulk and nanofilm amorphous samples in the paramagnetic phase. The application to nanofilms with emergent self-affine free interfaces requires a careful definition of the film "width" and its change due to the magnetostriction effect.

Influence of amorphous structure on polymorphism in vanadia

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

Stone, Kevin H.; Schelhas, Laura T.; Garten, Lauren M.

Normally we think of the glassy state as a single phase and therefore crystallization from chemically identical amorphous precursors should be identical. Here we show that the local structure of an amorphous precursor is distinct depending on the initial deposition conditions, resulting in significant differences in the final state material. Using grazing incidence total x-ray scattering, we have determined the local structure in amorphous thin films of vanadium oxide grown under different conditions using pulsed laser deposition (PLD). Here we show that the subsequent crystallization of films deposited using different initial PLD conditions result in the formation of different polymorphsmore » of VO 2. Ultimately this suggests the possibility of controlling the formation of metastable polymorphs by tuning the initial amorphous structure to different formation pathways.« less

Influence of amorphous structure on polymorphism in vanadia

DOE PAGES

Stone, Kevin H.; Schelhas, Laura T.; Garten, Lauren M.; ...

2016-07-13

Normally we think of the glassy state as a single phase and therefore crystallization from chemically identical amorphous precursors should be identical. Here we show that the local structure of an amorphous precursor is distinct depending on the initial deposition conditions, resulting in significant differences in the final state material. Using grazing incidence total x-ray scattering, we have determined the local structure in amorphous thin films of vanadium oxide grown under different conditions using pulsed laser deposition (PLD). Here we show that the subsequent crystallization of films deposited using different initial PLD conditions result in the formation of different polymorphsmore » of VO 2. Ultimately this suggests the possibility of controlling the formation of metastable polymorphs by tuning the initial amorphous structure to different formation pathways.« less

X-Ray Amorphous Phases in Antarctica Dry Valley Soils: Insight into Aqueous Alteration Processes on Mars?

NASA Technical Reports Server (NTRS)

Ming, D. W.; Morris, R. V.; Rampe, E. B.; Golden, D. C.; Quinn, J. E.

2015-01-01

The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 weight percentage) of X-ray amorphous materials in a windblown deposit (Rocknest) and in a sedimentary mudstone (Cumberland and John Klein) in Gale crater, Mars. On Earth, X-ray amorphous components are common in soils and sediments, but usually not as abundant as detected in Gale crater. One hypothesis for the abundant X-ray amorphous materials on Mars is limited interaction of liquid water with surface materials, kinetically inhibiting maturation to more crystalline phases. The objective of this study was to characterize the chemistry and mineralogy of soils formed in the Antarctica Dry Valleys, one of the driest locations on Earth. Two soils were characterized from different elevations, including a low elevation, coastal, subxerous soil in Taylor Valley and a high elevation, ultraxerous soil in University Valley. A variety of techniques were used to characterize materials from each soil horizon, including Rietveld analysis of X-ray diffraction data. For Taylor Valley soil, the X-ray amorphous component ranged from about 4 weight percentage in the upper horizon to as high as 15 weight percentage in the lowest horizon just above the permafrost layer. Transmission electron microscopy indicated that the presence of short-range ordered (SRO) smectite was the most likely candidate for the X-ray amorphous materials in the Taylor Valley soils. The SRO smectite is likely an aqueous alteration product of mica inherited from granitic materials during glaciation of Taylor Valley. The drier University Valley soils had lower X-ray amorphous contents of about 5 weight percentage in the lowest horizon. The X-ray amorphous materials in University Valley are attributed to nanoparticles of TiO2 and possibly amorphous SiO2. The high abundance of X-ray amorphous materials in Taylor Valley is surprising for one of the driest places on Earth. These materials may have been physically and chemical altered during soil formation, however, the limited interaction with water and low temperatures may result in the formation of "immature" X-ray amorphous or SRO materials. Perhaps, a similar process contributes to the formation of the high content of X-ray amorphous materials detected on Mars.

Kinetics and pathways for crystallization of amorphous mullite and YAG

NASA Astrophysics Data System (ADS)

Johnson, Bradley Richard

The crystallization behavior of quenched mullite (3Al2O 3•2SiO2) and YAG (Y3Al5O 12) composition glasses (made using containerless methods) were characterized with the ultimate goal of producing single crystal, structural, ceramic oxide fibers from these materials. The kinetics for crystallization were determined from thermal analysis experiments. From the results, time-temperature-transformation (TTT) curves were calculated. The crystallization pathways were determined by examining the crystal structure, microstructure, and chemical composition of heat treated specimens using x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A machine was also designed and built to facilitate controlled crystallization of amorphous fibers. Quenched, Y3Al5O12 composition beads crystallized at temperatures as low as 840°C. The as-received specimens contained a few, small YAG crystals, in addition to a mixture of different amorphous phases. The coexistence of two different amorphous phases of the same composition, but having different densities is termed polyamorphism, and this has been reported to occur in Y3Al5O12 composition quenched melts. Although various crystallization pathways have been reported for chemically synthesized YAG precursors, these specimens crystallized directly into YAG, which was the only phase formed. Quenched, 3Al2O3•2SiO2 composition mullite beads and fibers crystallized at temperatures as low as 920°C. Due to phase separation in the quenched melts, multiple phases with slightly different compositions and different crystallization activation energies crystallized. These phases were not equilibrium, 3:2 mullite, but metastable, alumina-rich, pseudotetragonal mullite. The residual, amorphous, silica-rich phase existed as numerous, 7--10 nm sized inclusions embedded within pseudotetragonal mullite. A large amount of internal strain was detected in pseudotetragonal mullite, and the source of this strain was suggested to be the embedded, silica-rich inclusions. Pseudotetragonal mullite gradually converted to equilibrium, orthorhombic, 3:2 mullite between 1000--1400°C. This was characterized by assimilation of the embedded, silica-rich inclusions and the elimination of internal strain. Additionally, recrystallization of numerous, small, strain- and inclusion-free, 3:2 mullite grains was observed to occur as the process proceeded to completion.

Non-crosslinked, amorphous, block copolymer electrolyte for batteries

DOEpatents

Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

2006-04-11

Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

Crystal plasticity modeling of β phase deformation in Ti-6Al-4V

NASA Astrophysics Data System (ADS)

Moore, John A.; Barton, Nathan R.; Florando, Jeff; Mulay, Rupalee; Kumar, Mukul

2017-10-01

Ti-6Al-4V is an alloy of titanium that dominates titanium usage in applications ranging from mass-produced consumer goods to high-end aerospace parts. The material’s structure on a microscale is known to affect its mechanical properties but these effects are not fully understood. Specifically, this work will address the effects of low volume fraction intergranular β phase on Ti-6Al-4V’s mechanical response during the transition from elastic to plastic deformation. A crystal plasticity-based finite element model is used to fully resolve the deformation of the β phase for the first time. This high fidelity model captures mechanisms difficult to access via experiments or lower fidelity models. The results are used to assess lower fidelity modeling assumptions and identify phenomena that have ramifications for failure of the material.

Influence of B4C-doping and high-energy ball milling on phase formation and critical current density of (Bi,Pb)-2223 HTS

NASA Astrophysics Data System (ADS)

Margiani, N. G.; Mumladze, G. A.; Adamia, Z. A.; Kuzanyan, A. S.; Zhghamadze, V. V.

2018-05-01

In this paper, the combined effects of B4C-doping and planetary ball milling on the phase evolution, microstructure and transport properties of Bi1.7Pb0.3Sr2Ca2Cu3Oy(B4C)x HTS with x = 0 ÷ 0.125 were studied through X-ray diffraction (XRD), scanning electron microscopy (SEM), resistivity and critical current density measurements. Obtained results have shown that B4C additive leads to the strong acceleration of high-Tc phase formation and substantial enhancement in Jc. High-energy ball milling seems to produce a more homogeneous distribution of refined doped particles in the (Bi,Pb)-2223 HTS which results in an improved intergranular flux pinning and better self-field Jc performance.

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

Liang, Linyun; Mei, Zhi-Gang; Yacout, Abdellatif M.

We have developed a mesoscale phase-field model for studying the effect of recrystallization on the gas-bubble-driven swelling in irradiated U-Mo alloy fuel. The model can simulate the microstructural evolution of the intergranular gas bubbles on the grain boundaries as well as the recrystallization process. Our simulation results show that the intergranular gas-bubble-induced fuel swelling exhibits two stages: slow swelling kinetics before recrystallization and rapid swelling kinetics with recrystallization. We observe that the recrystallization can significantly expedite the formation and growth of gas bubbles at high fission densities. The reason is that the recrystallization process increases the nucleation probability of gasmore » bubbles and reduces the diffusion time of fission gases from grain interior to grain boundaries by increasing the grain boundary area and decreasing the diffusion distance. The simulated gas bubble shape, size distribution, and density on the grain boundaries are consistent with experimental measurements. We investigate the effect of the recrystallization on the gas-bubble-driven fuel swelling in UMo through varying the initial grain size and grain aspect ratio. We conclude that the initial microstructure of fuel, such as grain size and grain aspect ratio, can be used to effectively control the recrystallization and therefore reduce the swelling in U-Mo fuel.« less

Hydrogen absorption of Pd/ZrO2 composites prepared from Zr65Pd35 and Zr60Pd35Pt5 amorphous alloys

NASA Astrophysics Data System (ADS)

Ozawa, Masakuni; Katsuragawa, Naoya; Hattori, Masatomo; Yogo, Toshinobu; Yamamura, Shin-ichi

2018-01-01

Metal-dispersed composites were derived from amorphous Zr65Pd35 and Zr65Pd30Pt5 alloys and their hydrogen absorption behavior was studied. X-ray diffractograms and scanning electron micrographs indicated that mixtures containing ZrO2, the metallic phase of Pd, and PdO were formed for both amorphous alloys heat-treated in air. In the composites, micron-sized Pd-based metal precipitates were embedded in a ZrO2 matrix after heat treatment at 800 °C in air. The hydrogen temperature-programmed reduction was applied to study the reactivity of hydrogen gas with the oxidized Zr65Pd35 and Zr65Pd30Pt5 materials. Rapid hydrogen absorption and release were observed on the composite derived from the amorphous alloy below 100 °C. The hydrogen pressure-concentration isotherm showed that the absorbed amount of hydrogen in materials depended on the formation of the Pd or Pt-doped Pd phase and its large interface area to the matrix in the nanocomposites. The results indicate the importance of the composite structure for the fabrication of a new type of hydrogen storage material prepared from amorphous alloys.

Field-Induced Crystalline-to-Amorphous Phase Transformation on the Si Nano-Apex and the Achieving of Highly Reliable Si Nano-Cathodes

PubMed Central

Huang, Yifeng; Deng, Zexiang; Wang, Weiliang; Liang, Chaolun; She, Juncong; Deng, Shaozhi; Xu, Ningsheng

2015-01-01

Nano-scale vacuum channel transistors possess merits of higher cutoff frequency and greater gain power as compared with the conventional solid-state transistors. The improvement in cathode reliability is one of the major challenges to obtain high performance vacuum channel transistors. We report the experimental findings and the physical insight into the field induced crystalline-to-amorphous phase transformation on the surface of the Si nano-cathode. The crystalline Si tip apex deformed to amorphous structure at a low macroscopic field (0.6~1.65 V/nm) with an ultra-low emission current (1~10 pA). First-principle calculation suggests that the strong electrostatic force exerting on the electrons in the surface lattices would take the account for the field-induced atomic migration that result in an amorphization. The arsenic-dopant in the Si surface lattice would increase the inner stress as well as the electron density, leading to a lower amorphization field. Highly reliable Si nano-cathodes were obtained by employing diamond like carbon coating to enhance the electron emission and thus decrease the surface charge accumulation. The findings are crucial for developing highly reliable Si-based nano-scale vacuum channel transistors and have the significance for future Si nano-electronic devices with narrow separation. PMID:25994377

Intergranular fracture of lithium fluoride-22 percent calcium fluoride hypereutectic salt at 800 K

NASA Technical Reports Server (NTRS)

Raj, Subramanium V.; Whittenberger, J. Daniel

1990-01-01

Substantial strain-hardening was noted during the initial stages of deformation in constant-velocity compression tests conducted on as-cast samples of the LiF-22 mol pct CaF2 hypereutectic salt at 800 K. The deformed specimens exhibited extensive grain-boundary cracking and cavitation, suggesting that such cracking, in conjunction with interfacial sliding, is important for cavity nucleation at grain boundaries and at the LiF-CaF2 interfaces. Cavity growth and interlinkage occur through the preferential failure of the weaker LiF phase.

Evolution of Grain Boundary Precipitates in an Al-Cu-Li Alloy During Aging

NASA Astrophysics Data System (ADS)

Ott, Noémie; Kairy, Shravan K.; Yan, Yuanming; Birbilis, Nick

2017-01-01

The grain boundary microstructure of Al-Cu-Li alloy AA2050 was investigated for different isothermal aging times to rationalize intergranular corrosion (IGC) characteristics. In the underaged condition, the dominant grain boundary precipitates are fine T1 (Al2CuLi). Extended aging revealed that grain boundaries were decorated by large T1 precipitates and S' phase (Al2CuMg), with S' growth not dimensionally constrained. Such a transition in the precipitate type at grain boundaries is a unique feature of the Al-Cu-Li system.

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.

Detecting phase separation of freeze-dried binary amorphous systems using pair-wise distribution function and multivariate data analysis.

PubMed

Chieng, Norman; Trnka, Hjalte; Boetker, Johan; Pikal, Michael; Rantanen, Jukka; Grohganz, Holger

2013-09-15

The purpose of this study is to investigate the use of multivariate data analysis for powder X-ray diffraction-pair-wise distribution function (PXRD-PDF) data to detect phase separation in freeze-dried binary amorphous systems. Polymer-polymer and polymer-sugar binary systems at various ratios were freeze-dried. All samples were analyzed by PXRD, transformed to PDF and analyzed by principal component analysis (PCA). These results were validated by differential scanning calorimetry (DSC) through characterization of glass transition of the maximally freeze-concentrate solute (Tg'). Analysis of PXRD-PDF data using PCA provides a more clear 'miscible' or 'phase separated' interpretation through the distribution pattern of samples on a score plot presentation compared to residual plot method. In a phase separated system, samples were found to be evenly distributed around the theoretical PDF profile. For systems that were miscible, a clear deviation of samples away from the theoretical PDF profile was observed. Moreover, PCA analysis allows simultaneous analysis of replicate samples. Comparatively, the phase behavior analysis from PXRD-PDF-PCA method was in agreement with the DSC results. Overall, the combined PXRD-PDF-PCA approach improves the clarity of the PXRD-PDF results and can be used as an alternative explorative data analytical tool in detecting phase separation in freeze-dried binary amorphous systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Comparative surface dynamics of amorphous and semicrystalline polymer films

PubMed Central

Becker, James S.; Brown, Ryan D.; Killelea, Daniel R.; Yuan, Hanqiu; Sibener, S. J.

2011-01-01

The surface dynamics of amorphous and semicrystalline polymer films have been measured using helium atom scattering. Time-of-flight data were collected to resolve the elastic and inelastic scattering components in the diffuse scattering of neutral helium atoms from the surface of a thin poly(ethylene terephthalate) film. Debye–Waller attenuation was observed for both the amorphous and semicrystalline phases of the polymer by recording the decay of elastically scattered helium atoms with increasing surface temperature. Thermal attenuation measurements in the specular scattering geometry yielded perpendicular mean-square displacements of 2.7•10-4 Å2 K-1 and 3.1•10-4 Å2 K-1 for the amorphous and semicrystalline surfaces, respectively. The semicrystalline surface was consistently ∼15% softer than the amorphous across a variety of perpendicular momentum transfers. The Debye–Waller factors were also measured at off-specular angles to characterize the parallel mean-square displacements, which were found to increase by an order of magnitude over the perpendicular mean-square displacements for both surfaces. In contrast to the perpendicular motion, the semicrystalline state was ∼25% stiffer than the amorphous phase in the surface plane. These results were uniquely accessed through low-energy neutral helium atom scattering due to the highly surface-sensitive and nonperturbative nature of these interactions. The goal of tailoring the chemical and physical properties of complex advanced materials requires an improved understanding of interfacial dynamics, information that is obtainable through atomic beam scattering methods. PMID:20713734

Self-Organization of Amorphous Carbon Nanocapsules into Diamond Nanocrystals Driven by Self-Nanoscopic Excessive Pressure under Moderate Electron Irradiation without External Heating.

PubMed

Wang, Chengbing; Ling, San; Yang, Jin; Rao, Dewei; Guo, Zhiguang

2018-01-01

Phase transformation between carbon allotropes usually requires high pressures and high temperatures. Thus, the development of low-temperature phase transition approaches between carbon allotropes is highly desired. Herein, novel amorphous carbon nanocapsules are successfully synthesized by pulsed plasma glow discharge. These nanocapsules are comprised of highly strained carbon clusters encapsulated in a fullerene-like carbon matrix, with the formers serving as nucleation sites. These nucleation sites favored the formation of a diamond unit cell driven by the self-nanoscopic local excessive pressure, thereby significantly decreasing the temperature required for its transformation into a diamond nanocrystal. Under moderate electron beam irradiation (10-20 A cm -2 ) without external heating, self-organization of the energetic carbon clusters into diamond nanocrystals is achieved, whereas the surrounding fullerene-like carbon matrix remains nearly unchanged. Molecular dynamics simulations demonstrate that the defective rings as the active sites dominate the phase transition of amorphous carbon to diamond nanocrystal. The findings may open a promising route to realize phase transformation between carbon allotropes at a lower temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Induced anisotropy in FeCo-based nanocomposites: Early transition metal content dependence

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

Shen, S; DeGeorge, V; Ohodnicki, PR

2014-05-07

Soft magnetic nanocomposites variants of FeCo-based (HTX002) alloys (Fe65Co35)(81+x)B12Nb4-xSi2Cu1, exhibiting high inductions (up to 1.9 T), low losses, and high temperature stability are studied for high frequency inductors and current sensors. For alloys with x 0, 1, 1.5, 2, and 3, we report field induced anisotropy, K-U, after annealing at temperatures of 340-450 degrees C for 1 h in a 2 T transverse magnetic field. The anisotropy field, H-K, measured by AC permeametry on toroidal cores, and by first order reversal curves on square sections of ribbon, decreases with annealing temperature and saturates at high annealing temperatures suggesting a nanostructuremore » related anisotropy mechanism in which the amorphous phase exhibits a higher H-K than the crystalline phase. A high saturation induction nanocrystalline phase and high H-K amorphous phase were achieved by low temperature annealing resulting in a value of K-U exceeding 14 X 10(3) erg/cm(3), more than twice that reported previously for Fe-rich amorphous and nanocomposite alloys. (C) 2014 AIP Publishing LLC.« less

Behavior of Sn atoms in GeSn thin films during thermal annealing: Ex-situ and in-situ observations

NASA Astrophysics Data System (ADS)

Takase, Ryohei; Ishimaru, Manabu; Uchida, Noriyuki; Maeda, Tatsuro; Sato, Kazuhisa; Lieten, Ruben R.; Locquet, Jean-Pierre

2016-12-01

Thermally induced crystallization processes for amorphous GeSn thin films with Sn concentrations beyond the solubility limit of the bulk crystal Ge-Sn binary system have been examined by X-ray photoelectron spectroscopy, grazing incidence X-ray diffraction, and (scanning) transmission electron microscopy. We paid special attention to the behavior of Sn before and after recrystallization. In the as-deposited specimens, Sn atoms were homogeneously distributed in an amorphous matrix. Prior to crystallization, an amorphous-to-amorphous phase transformation associated with the rearrangement of Sn atoms was observed during heat treatment; this transformation is reversible with respect to temperature. Remarkable recrystallization occurred at temperatures above 400 °C, and Sn atoms were ejected from the crystallized GeSn matrix. The segregation of Sn became more pronounced with increasing annealing temperature, and the ejected Sn existed as a liquid phase. It was found that the molten Sn remains as a supercooled liquid below the eutectic temperature of the Ge-Sn binary system during the cooling process, and finally, β-Sn precipitates were formed at ambient temperature.

Correlative transmission electron microscopy and electrical properties study of switchable phase-change random access memory line cells

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

Oosthoek, J. L. M.; Kooi, B. J., E-mail: B.J.Kooi@rug.nl; Voogt, F. C.

2015-02-14

Phase-change memory line cells, where the active material has a thickness of 15 nm, were prepared for transmission electron microscopy (TEM) observation such that they still could be switched and characterized electrically after the preparation. The result of these observations in comparison with detailed electrical characterization showed (i) normal behavior for relatively long amorphous marks, resulting in a hyperbolic dependence between SET resistance and SET current, indicating a switching mechanism based on initially long and thin nanoscale crystalline filaments which thicken gradually, and (ii) anomalous behavior, which holds for relatively short amorphous marks, where initially directly a massive crystalline filament ismore » formed that consumes most of the width of the amorphous mark only leaving minor residual amorphous regions at its edges. The present results demonstrate that even in (purposely) thick TEM samples, the TEM sample preparation hampers the probability to observe normal behavior and it can be debated whether it is possible to produce electrically switchable TEM specimen in which the memory cells behave the same as in their original bulk embedded state.« less

Correlative transmission electron microscopy and electrical properties study of switchable phase-change random access memory line cells

NASA Astrophysics Data System (ADS)

Oosthoek, J. L. M.; Voogt, F. C.; Attenborough, K.; Verheijen, M. A.; Hurkx, G. A. M.; Gravesteijn, D. J.; Kooi, B. J.

2015-02-01

Phase-change memory line cells, where the active material has a thickness of 15 nm, were prepared for transmission electron microscopy (TEM) observation such that they still could be switched and characterized electrically after the preparation. The result of these observations in comparison with detailed electrical characterization showed (i) normal behavior for relatively long amorphous marks, resulting in a hyperbolic dependence between SET resistance and SET current, indicating a switching mechanism based on initially long and thin nanoscale crystalline filaments which thicken gradually, and (ii) anomalous behavior, which holds for relatively short amorphous marks, where initially directly a massive crystalline filament is formed that consumes most of the width of the amorphous mark only leaving minor residual amorphous regions at its edges. The present results demonstrate that even in (purposely) thick TEM samples, the TEM sample preparation hampers the probability to observe normal behavior and it can be debated whether it is possible to produce electrically switchable TEM specimen in which the memory cells behave the same as in their original bulk embedded state.

Enhanced Azo-Dyes Degradation Performance of Fe-Si-B-P Nanoporous Architecture

PubMed Central

Weng, Nan; Wang, Feng; Qin, Fengxiang; Tang, Wanying; Dan, Zhenhua

2017-01-01

Nanoporous structures were fabricated from Fe76Si9B10P5 amorphous alloy annealed at 773 K by dealloying in 0.05 M H2SO4 solution, as a result of preferential dissolution of α-Fe grains in form of the micro-coupling cells between α-Fe and cathodic residual phases. Nanoporous Fe-Si-B-P powders exhibit much better degradation performance to methyl orange and direct blue azo dyes compared with gas-atomized Fe76Si9B10P5 amorphous powders and commercial Fe powders. The degradation reaction rate constants of nanoporous powders are almost one order higher than those of the amorphous counterpart powders and Fe powders, accompanying with lower activation energies of 19.5 and 26.8 kJ mol−1 for the degradation reactions of methyl orange and direct blue azo dyes, respectively. The large surface area of the nanoporous structure, and the existence of metalloids as well as residual amorphous phase with high catalytic activity are responsible for the enhanced azo-dyes degradation performance of the nanoporous Fe-Si-B-P powders. PMID:28846622

Amorphization and Directional Crystallization of Metals Confined in Carbon Nanotubes Investigated by in Situ Transmission Electron Microscopy.

PubMed

Tang, Dai-Ming; Ren, Cui-Lan; Lv, Ruitao; Yu, Wan-Jing; Hou, Peng-Xiang; Wang, Ming-Sheng; Wei, Xianlong; Xu, Zhi; Kawamoto, Naoyuki; Bando, Yoshio; Mitome, Masanori; Liu, Chang; Cheng, Hui-Ming; Golberg, Dmitri

2015-08-12

The hollow core of a carbon nanotube (CNT) provides a unique opportunity to explore the physics, chemistry, biology, and metallurgy of different materials confined in such nanospace. Here, we investigate the nonequilibrium metallurgical processes taking place inside CNTs by in situ transmission electron microscopy using CNTs as nanoscale resistively heated crucibles having encapsulated metal nanowires/crystals in their channels. Because of nanometer size of the system and intimate contact between the CNTs and confined metals, an efficient heat transfer and high cooling rates (∼10(13) K/s) were achieved as a result of a flash bias pulse followed by system natural quenching, leading to the formation of disordered amorphous-like structures in iron, cobalt, and gold. An intermediate state between crystalline and amorphous phases was discovered, revealing a memory effect of local short-to-medium range order during these phase transitions. Furthermore, subsequent directional crystallization of an amorphous iron nanowire formed by this method was realized under controlled Joule heating. High-density crystalline defects were generated during crystallization due to a confinement effect from the CNT and severe plastic deformation involved.

In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

DOEpatents

Kim, Choong Paul; Hays, Charles C.; Johnson, William L.

2004-03-23

A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

DOEpatents

Kim, Choong Paul [Northridge, CA; Hays, Charles C [Pasadena, CA; Johnson, William L [Pasadena, CA

2007-07-17

A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

Crystallization engineering as a route to epitaxial strain control

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

Akbashev, Andrew R.; Plokhikh, Aleksandr V.; Barbash, Dmitri

2015-10-01

The controlled synthesis of epitaxial thin films offers opportunities for tuning their functional properties via enabling or suppressing strain relaxation. Examining differences in the epitaxial crystallization of amorphous oxide films, we report on an alternate, low-temperature route for strain engineering. Thin films of amorphous Bi–Fe–O were grown on (001)SrTiO{sub 3} and (001)LaAlO{sub 3} substrates via atomic layer deposition. In situ X-ray diffraction and X-ray photoelectron spectroscopy studies of the crystallization of the amorphous films into the epitaxial (001)BiFeO{sub 3} phase reveal distinct evolution profiles of crystallinity with temperature. While growth on (001)SrTiO{sub 3} results in a coherently strained film, themore » same films obtained on (001)LaAlO{sub 3} showed an unstrained, dislocation-rich interface, with an even lower temperature onset of the perovskite phase crystallization than in the case of (001)SrTiO{sub 3}. Our results demonstrate how the strain control in an epitaxial film can be accomplished via its crystallization from the amorphous state.« less

Solubilization of Genistein in Poly(Ethylene Glycol) via Eutectic Crystal Melting

NASA Astrophysics Data System (ADS)

Buddhiranon, Sasiwimon; Kyu, Thein

2012-02-01

Genistein (5,7,4'-trihydroxyisoflavone) is a phytoestrogen found in soybean. It possesses various biological/pharmacological functions, e.g., tyrosine kinase inhibitory, anticarcinogenic, antioxidant, anti-inflammatory, and anti-microbial activities. However, genistein has poor water solubility and skin permeability, which have seemingly prohibited the progress to preclinical evaluation. Eutectic melting approach has been performed as a means of solubilizing genistein in poly(ethylene glycol) (PEG). Eutectic phase diagrams of blends containing genistein and PEG having three different molecular weights, i.e., 44k, 7k, and 500 g/mol, were established by means of DSC and compared with the theoretical liquidus and solidus lines, calculated self-consistently by taking into consideration all interactions including amorphous-amorphous, crystal-amorphous, amorphous-crystal, and crystal-crystal interactions. The eutectic temperatures were found to decrease with decreasing molecular weight of PEG. Guided by the phase diagram, it was found that genistein can be dissolved in PEG500 up to ˜7 wt% at room temperature. More importantly, the solubility of genistein in PEG can be improved to meet the end-use criteria of the PEG/genistein mixtures.

Some aspects of thermomechanical fatigue of AISI 304L stainless steel: Part I. creep- fatigue damage

NASA Astrophysics Data System (ADS)

Zauter, R.; Christ, H. J.; Mughrabi, H.

1994-02-01

Thermomechanical fatigue (TMF) tests on the austenitic stainless steel AISI 304L have been conducted under “true≓ plastic-strain control in vacuum. This report considers the damage oc-curring during TMF loading. It is shown how the temperature interval and the phasing (in-phase, out-of-phase) determine the mechanical response and the lifetime of the specimens. If creep-fatigue interaction takes place during in-phase cycling, the damage occurs inside the ma-terial, leading to intergranular cracks which reduce the lifetime considerably. Out-of-phase cy-cling inhibits creep-induced damage, and no lifetime reduction occurs, even if the material is exposed periodically to temperatures in the creep regime. A formula is proposed which allows prediction of the failure mode, depending on whether creep-fatigue damage occurs or not. At a given strain rate, the formula is able to estimate the temperature of transition between pure fatigue and creep-fatigue damage.

An Electrochemical Framework to Explain Intergranular Stress Corrosion Cracking in an Al-5.4%Cu-0.5%Mg-0.5%Ag Alloy

NASA Technical Reports Server (NTRS)

Little, D. A.; Connolly, B. J.; Scully, J. R.

2001-01-01

A modified version of the Cu-depletion electrochemical framework was used to explain the metallurgical factor creating intergranular stress corrosion cracking susceptibility in an aged Al-Cu-Mg-Ag alloy, C416. This framework was also used to explain the increased resistance to intergranular stress corrosion cracking in the overaged temper. Susceptibility in the under aged and T8 condition is consistent with the grain boundary Cu-depletion mechanism. Improvements in resistance of the T8+ thermal exposure of 5000 h at 225 F (T8+) compared to the T8 condition can be explained by depletion of Cu from solid solution.

Solid state amorphization in the Al-Fe binary system during high energy milling

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

Urban, P., E-mail: purban@us.es; Montes, J. M.; Cintas, J.

2013-12-16

In the present study, mechanical alloying (MA) of Al75Fe25 elemental powders mixture was carried out in argon atmosphere, using a high energy attritor ball mill. The microstructure of the milled products at different stages of milling was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The results showed that the amorphous phase content increased by increasing the milling time, and after 50 hours the amorphization process became complete. Heating the samples resulted in the crystallization of the synthesized amorphous alloys and the appearance of the equilibrium intermetallic compounds Al{sub 5}Fe{submore » 2}.« less

Nanoscale amorphization of GeTe nanowire with conductive atomic force microscope.

PubMed

Kim, JunHo

2014-10-01

We fabricated GeTe nanowires by using Au catalysis mediated vapor-liquid-solid method. The fabricated nanowires were confirmed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. For a nanowire with - 150 nm diameter, we performed amorphization experiment with conductive atomic force microscope. We examined the structural change of the nanowire with several bias voltages from 0 V to 10 V. Above bias voltage of 6-7 V, some points of the nanowire showed transition to amorphous phase. The consumed energy for the amorphization was estimated to be 4-5 nJ, which was close to the other result of nanowire tested with a four probe device.

Formation of budesonide/α-lactose glass solutions by ball-milling

NASA Astrophysics Data System (ADS)

Dudognon, E.; Willart, J. F.; Caron, V.; Capet, F.; Larsson, T.; Descamps, M.

2006-04-01

The possibility to obtain amorphous budesonide stabilised by blending with an excipient characterised by a higher glass transition temperature, namely α-lactose, has been studied. We carried out the mixing of the two compounds at room temperature by ball-milling. The four obtained blends (containing, respectively, 10, 30, 50 and 70% w of budesonide) are X-ray amorphous and exhibit a single glass transition located between the ones of pure milled crystalline compounds. This revealed that the two amorphous phases are miscible whatever the composition and sufficiently mixed to relax as a whole. Ball-milling thus appears as a powerful tool to form amorphous molecular alloys with enhanced stability properties.

High pressure polymorphs and amorphization of upconversion host material NaY(WO{sub 4}){sub 2}

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

Hong, Fang; Yue, Binbin, E-mail: yuebb@hpstar.ac.cn, E-mail: chenbin@hpstar.ac.cn; The Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd, Berkeley, California 94720

2016-07-25

The pressure effect on the structural change of upconversion host material NaY(WO{sub 4}){sub 2} was studied by using in-situ synchrotron X-ray diffraction. A transition from the initial scheelite phase to the M-fergusonite phase occurs near 10 GPa, and another phase transition is found near 27.5 GPa, which could be an isostructural transition without symmetry change. The sample becomes amorphous when the pressure is fully released from high pressure. This work demonstrates the possibility of synthesizing various polymorph structures for non-linear optical applications with a high pressure, chemical doping, or strained thin-film nanostructure process.

On the evolution and activity of cometary nuclei.

PubMed

Prialnik, D; Bar-Nun, A

1987-02-15

The thermal evolution of a spherical cometary nucleus (initial radius of 2.5 km), composed initially of very cold amorphous ice and moving in comet Halley's orbit, is simulated numerically for 280 revolutions. It is found that the phase transition from amorphous to crystalline ice constitutes a major internal heat source. The transition does not occur continuously, but in five distinct rounds, during the following revolutions: 1, 7, 40-41, 110-112, and 248-252. Due to the (slow) heating of the amorphous ice between crystallization rounds, the phase transition front advances into the nucleus to progressively greater depths: 36 m on the first round, and then 91 m, 193 m, 381 m, and 605 m respectively. Each round of crystallization starts when when the boundary between amorphous and crystalline ice is brought to approximately 15 m below the surface, as the nucleus radius decreases due to sublimation. At the time of crystallization, the temperature of the transformed ice rises to 180 K. According to experimental studies of gas-laden amorphous ice, a large fraction of the gas trapped in the ice at low temperatures is released. Whereas some of the released gas may find its way out through cracks in the crystalline ice layer, the rest is expected to accumulate in gas pockets that may eventually explode, forming "volcanic calderas." The gas-laden amorphous ice thus exposed may be a major source of gas and dust jets into the coma, such as those observed on comet Halley by the Giotto spacecraft. The activity of new comets and, possibly, cometary outbursts and splits may also be explained in terms of explosive gas release following the transition from amorphous to crystalline ice.

The effect of high energy concentration source irradiation on structure and properties of Fe-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Pilarczyk, Wirginia

2016-06-01

Metallic glasses exhibit metastable structure and maintain this relatively stable amorphous state within certain temperature range. High intensity laser beam was used for the surface irradiation of Fe-Co-B-Si-Nb bulk metallic glasses. The variable parameter was laser beam pulse energy. For the analysis of structure and properties of bulk metallic glasses and their surface after laser remelting the X-ray analysis, microscopic observation and test of mechanical properties were carried out. Examination of the nanostructure of amorphous materials obtained by high pressure copper mold casting method and the irradiated with the use of TITAN 80-300 HRTEM was carried out. Nanohardness and reduced Young's modulus of particular amorphous and amorphous-crystalline material zone of the laser beam were examined with the use of Hysitron TI950 Triboindenter nanoindenter and with the use of Berkovich's indenter. The XRD and microscopic analysis showed that the test material is amorphous in its structure before irradiation. Microstructure observation with electron transmission microscopy gave information about alloy crystallization in the irradiated process. Identification of given crystal phases allows to determine the kind of crystal phases created in the first place and also further changes of phase composition of alloy. The main value of the nanohardness of the surface prepared by laser beam has the order of magnitude similar to bulk metallic glasses formed by casting process irrespective of the laser beam energy used. Research results analysis showed that the area between parent material and fusion zone is characterized by extraordinarily interesting structure which is and will be the subject of further analysis in the scope of bulk metallic glasses amorphous structure and high energy concentration source. The main goal of this work is the results' presentation of structure and chosen properties of the selected bulk metallic glasses after casting process and after irradiation process employing the high energy concentration sources.

Effect of Solute Segregation on Fracture Toughness in a Ni-Cr Steel

NASA Astrophysics Data System (ADS)

Kameda, Jun

1981-12-01

A study has been made of the influence of intergranular solute segregation on fracture toughness K1c in a series of Ni-Cr steels individually doped with Sb, Sn, and P. By means of toughness measurements in steels having two different intergranular Sb distributions, of measurements of acoustic emissions and of scanning electron micrographs of a load-interrupted and post-test-fatigued specimen, the values of K1c, computed from the “pop-in” load of the load vs clip gauge displacement curves, are found to represent the formation of many patches of contiguous intergranular microcracks ahead of the precrack. The present experiments demonstrate that in the early stage of solute segregation, K1c decreases more substantially than does the strength of grain boundaries σ* (measured in the notched bar tests), although the embrittlement effects of metalloid elements are the same order for both K1c and σ*. A proposed model for the stress-gradient-control of brittle fracture supports the finding that the measurements of K1c give a distorted view of the progress of intergranular embrittlement.

Pore-scale Modeling of CO2 Local Trapping in Heterogeneous Porous Media with Inter-granular Cements

NASA Astrophysics Data System (ADS)

Wang, D.; Li, Y.

2017-12-01

Based on pore-scale modeling of CO2/brine multiphase flow in heterogeneous porous media with inter-granular cements, we numerically analyze the effects of cement-modified pore structure on CO2 local trapping. Results indicate: 1) small pore throat is the main reason for causing CO2 local trapping in front of low-porosity layers (namely dense layers) formed by inter-granular cements; 2) in the case of the same pore throat size, the smaller particle size can increase the number of flow paths for CO2 plume and equivalently enhances local permeability, which may counteract the impediment of high capillary pressure on CO2 migration to some extent and consequently disables CO2 local capillary trapping; 3) the isolated pores by inter-granular cements can lead to dramatic reduction of CO2 saturation inside the dense layers, whereas the change of connectivity of some pores due to the cements can increase CO2 accumulation in front of the dense layers by lowering the displacement area of CO2 plume.

A Three-Stage Mechanistic Model for Solidification Cracking During Welding of Steel

NASA Astrophysics Data System (ADS)

Aucott, L.; Huang, D.; Dong, H. B.; Wen, S. W.; Marsden, J.; Rack, A.; Cocks, A. C. F.

2018-03-01

A three-stage mechanistic model for solidification cracking during TIG welding of steel is proposed from in situ synchrotron X-ray imaging of solidification cracking and subsequent analysis of fracture surfaces. Stage 1—Nucleation of inter-granular hot cracks: cracks nucleate inter-granularly in sub-surface where maximum volumetric strain is localized and volume fraction of liquid is less than 0.1; the crack nuclei occur at solute-enriched liquid pockets which remain trapped in increasingly impermeable semi-solid skeleton. Stage 2—Coalescence of cracks via inter-granular fracture: as the applied strain increases, cracks coalesce through inter-granular fracture; the coalescence path is preferential to the direction of the heat source and propagates through the grain boundaries to solidifying dendrites. Stage 3—Propagation through inter-dendritic hot tearing: inter-dendritic hot tearing occurs along the boundaries between solidifying columnar dendrites with higher liquid fraction. It is recommended that future solidification cracking criterion shall be based on the application of multiphase mechanics and fracture mechanics to the failure of semi-solid materials.

Basalt Weathering in a Cold and Icy Climate: Three Sisters, Oregon as an Analog for Early Mars

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Horgan, B.; Smith, R. J.; Scudder, N. A.; Rutledge, A. M.; Bamber, E.; Morris, R. V.

2017-01-01

There is abundant evidence for liquid water on early Mars, but the debate remains whether early Mars was warm and wet or cold and icy with punctuated periods of melting. To further investigate the hypothesis of a cold and icy early Mars, we collected rocks and sediments from the Collier and Diller glacial valleys in the Three Sisters volcanic complex in Oregon. We analyzed rocks and sediments with X-ray diffraction (XRD), scanning and transmission electron microscopies with energy dispersive spectroscopy (SEM, TEM, EDS), and visible, short-wave infrared (VSWIR) and thermal-IR (TIR) spectroscopies to characterize chemical weathering and sediment transport through the valleys. Here, we focus on the composition and mineralogy of the weathering products and how they compare to those identified on the martian surface. Phyllosilicates (smectite), zeolites, and poorly crystalline phases were discovered in pro- and supra-glacial sediments, whereas Si-rich regelation films were found on hand samples and boulders in the proglacial valleys. Most phyllosilicates and zeolites are likely detrital, originating from hydrothermally altered units on North Sister. TEM-EDS analyses of the <2 um size fraction of glacial flour samples demonstrate a variety of poorly crystalline (i.e., no long-range crystallographic order) phases: iron oxides, devitrified volcanic glass, and Fe-Si-Al phases. The CheMin XRD on the Curiosity rover in Gale crater has identified significant amounts of X-ray amorphous materials in all samples measured to date. The amorphous component is likely a combination of silicates, iron oxides, and sulfates. Although we have not yet observed amorphous sulfate in the samples from Three Sisters, the variety of poorly crystalline weathering products found at this site is consistent with the variable composition of the X-ray amorphous component identified by CheMin. We suggest that these amorphous phases on Mars could have formed in a similarly cold and icy environment.

Stability of Cr Remediation Products Linked to Duration of Bioremediation.

NASA Astrophysics Data System (ADS)

Miller, L. G.; Bobb, C.; Bennett, S.; Izbicki, J. A.

2017-12-01

Groundwater and alluvium beneath Hinkley Valley, Mojave Desert, California contain elevated levels of anthropogenic Cr(VI). In-situ remediation (ISR) using ethanol as an electron donor is employed at the site to reduce soluble, toxic, Cr(VI) to insoluble and non-hazardous Cr(III). We conducted year-long experiments to determine the fate of isotopically-labeled 50Cr tracer within microcosms consisting of sealed batch reactors containing aquifer material and groundwater from within and near the mapped Cr(VI) plume. Ethanol was added periodically to the reactors to drive biologically mediated reduction of Cr(VI). Reduction and sorption of 50Cr tracer on the solid matrix was examined by selective extractions designed to monitor operationally-defined weakly sorbed, specifically sorbed, amorphous, and well-crystalized strong-acid extractable phases. Recovery of the 50Cr tracer by ICP-MS analysis of each extract revealed the degree of mineralization of the added 50Cr. Initially, the tracer was distributed evenly between the aqueous and weakly sorbed phases, with little present in the strongly sorbed, amorphous or crystalline phases. After several months, most 50Cr was incorporated within the amorphous fraction and by one year increasing amounts were associated with the crystalline phase. Artificial substrates also were prepared as experimental controls. Artificial substrates showed similar trends; however less 50Cr was associated with amorphous Fe in acid-washed Ottowa sand coated with 2-line ferrihydrite than in aquifer sediments. Washed sand without ferrihydrite reacted with site water sorbed very little 50Cr, and no 50Cr was found in the amorphous fraction; however some was converted to the crystalline form with time. This suggests that groundwater-borne organisms alone were capable of reducing Cr(VI) to Cr(III) with ethanol in the absence of Fe(II). A planned metagenomics study of materials from these experiments is expected to highlight changes in microbial community composition and diversity as ISR progresses. Our experimental results bode well for the permanency of Cr sequestration by ISR; that is, Cr solubilization by re-oxidation may be less likely if reduced Cr is bound in more recalcitrant phases via extended reduction.

Height-dependent Velocity Structure of Photospheric Convection in Granules and Intergranular Lanes with Hinode /SOT

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

Oba, T.; Iida, Y.; Shimizu, T., E-mail: oba.takayoshi@ac.jaxa.jp

The solar photosphere is the visible surface of the Sun, where many bright granules, surrounded by narrow dark intergranular lanes, are observed everywhere. The granular pattern is a manifestation of convective motion at the photospheric level, but its velocity structure in the height direction is poorly understood observationally. Applying bisector analysis to a photospheric spectral line recorded by the Hinode Solar Optical Telescope, we derived the velocity structure of the convective motion in granular regions and intergranular lanes separately. The amplitude of motion of the convective material decreases from 0.65 to 0.40 km s{sup −1} as the material rises inmore » granules, whereas the amplitude of motion increases from 0.30 to 0.50 km s{sup −1} as it descends in intergranular lanes. These values are significantly larger than those obtained in previous studies using bisector analysis. The acceleration of descending materials with depth is not predicted from the convectively stable condition in a stratified atmosphere. Such convective instability can be developed more efficiently by radiative cooling and/or a gas pressure gradient, which can control the dynamical behavior of convective material in intergranular lanes. Our analysis demonstrated that bisector analysis is a useful method for investigating the long-term dynamic behavior of convective material when a large number of pixels is available. In addition, one example is the temporal evolution of granular fragmentation, in which downflowing material develops gradually from a higher layer downward.« less

Fractography of poly(methyl methacrylates).

PubMed

Kusy, R P; Turner, D T

1975-07-01

For convenience in clinical manipulation, it is the practice to fabricate PMMA protheses from mixtures of powder and monomer. When the monomer is subsequently polymerized an unusual 2-phase polymeric material results in which grains of PMMA are dispersed in a matrix of the same polymer. The mechanical properties of the 2-phase materials are inferior in certain respects relative to 1-phase polymers. The purpose of the present work is to evaluate the failure of 2-phase materials by microscopical examination of their fracture surfaces. A granular microstructure was clearly distinguishable and a distinction made between materials which fail exclusively by transgranular fracture and others which additionally exhibit intergranular fracture. In order to interpret markings observed on the fracture surfaces of the complex 2-phase systems a study was made of the influence of molecular weight on the fractography of 1-phase PMMA. Molecular weight was reduced by degradation of samples by exposure to gamma-rays. The spacing of periodic rib markings on fracture surfaces was found to decrease with molecular weight and this relationship used to provide an estimate of the molecular weight of polymer in the matrix of 2-phase materials.

Equation of state and pressure induced amorphization of beta-boron from X-ray measurements up to 100 GPa.

PubMed

Sanz, Delia Nieto; Loubeyre, Paul; Mezouar, Mohamed

2002-12-09

The equation of state of boron has been measured up to 100 GPa by single-crystal x-ray diffraction with helium as the pressure transmitting medium. Rhombohedral beta-boron is the stable structure up to 100 GPa under hydrostatic conditions. Nonhydrostatic stress stabilizes a different rhombohedral structure. At about 100 GPa a pressure-induced amorphization is observed. The amorphous phase can be quenched to ambient pressure. An explanation is proposed based on the different stability under pressure between intraicosahedra and intericosahedra bonds.

Clathrate hydrate formation in amorphous cometary ice analogs in vacuo

NASA Technical Reports Server (NTRS)

Blake, David; Allamandola, Louis; Sandford, Scott; Hudgins, Doug; Freund, Friedemann

1991-01-01

Experiments conducted in clathrate hydrates with a modified electron microscope have demonstrated the possibility of such compounds' formation during the warming of vapor-deposited amorphous ices in vacuo, through rearrangements in the solid state. Subsolidus crystallization of compositionally complex amorphous ices may therefore be a general and ubiquitous process. Phase separations and microporous textures thus formed may be able to account for such anomalous cometary phenomena as the release of gas at large radial distances from the sun and the retention of volatiles to elevated temperatures.

A case study of real-time monitoring of solid-state phase transformations in acoustically levitated particles using near infrared and Raman spectroscopy.

PubMed

Rehder, Sönke; Wu, Jian X; Laackmann, Julian; Moritz, Hans-Ulrich; Rantanen, Jukka; Rades, Thomas; Leopold, Claudia S

2013-01-23

The objective of this study was to monitor the amorphous-to-crystalline solid-state phase transformation kinetics of the model drug ibuprofen with spectroscopic methods during acoustic levitation. Chemical and physical information was obtained by real-time near infrared (NIRS) and Raman spectroscopy measurements. The recrystallisation kinetic parameters (overall recrystallisation rate constant β and the time needed to reach 50% of the equilibrated level t(50)), were determined using a multivariate curve resolution approach. The acoustic levitation device coupled with non-invasive spectroscopy enabled monitoring of the recrystallisation process of the difficult-to-handle (adhesive) amorphous sample. The application of multivariate curve resolution enabled isolation of the underlying pure spectra, which corresponded well with the reference spectra of amorphous and crystalline ibuprofen. The recrystallisation kinetic parameters were estimated from the recrystallisation profiles. While the empirical recrystallisation rate constant determined by NIR and Raman spectroscopy were comparable, the lag time for recrystallisation was significantly lower with Raman spectroscopy as compared to NIRS. This observation was explained by the high energy density of the Raman laser beam, which might have led to local heating effects of the sample and thus reduced the recrystallisation onset time. It was concluded that acoustic levitation with NIR and Raman spectroscopy combined with multivariate curve resolution allowed direct determination of the recrystallisation kinetics of amorphous drugs and thus is a promising technique for monitoring solid-state phase transformations of adhesive small-sized samples during the early phase of drug development. Copyright © 2012 Elsevier B.V. All rights reserved.

Structural Analyses of Phase Stability in Amorphous and Partially Crystallized Ge-Rich GeTe Films Prepared by Atomic Layer Deposition.

PubMed

Gwon, Taehong; Mohamed, Ahmed Yousef; Yoo, Chanyoung; Park, Eui-Sang; Kim, Sanggyun; Yoo, Sijung; Lee, Han-Koo; Cho, Deok-Yong; Hwang, Cheol Seong

2017-11-29

The local bonding structures of Ge x Te 1-x (x = 0.5, 0.6, and 0.7) films prepared through atomic layer deposition (ALD) with Ge(N(Si(CH 3 ) 3 ) 2 ) 2 and ((CH 3 ) 3 Si) 2 Te precursors were investigated using Ge K-edge X-ray absorption spectroscopy (XAS). The results of the X-ray absorption fine structure analyses show that for all of the compositions, the as-grown films were amorphous with a tetrahedral Ge coordination of a mixture of Ge-Te and Ge-Ge bonds but without any signature of Ge-GeTe decomposition. The compositional evolution in the valence band electronic structures probed through X-ray photoelectron spectroscopy suggests a substantial chemical influence of additional Ge on the nonstoichiometric GeTe. This implies that the ALD process can stabilize Ge-abundant bonding networks like -Te-Ge-Ge-Te- in amorphous GeTe. Meanwhile, the XAS results on the Ge-rich films that had undergone post-deposition annealing at 350 °C show that the parts of the crystalline Ge-rich GeTe became separated into Ge crystallites and rhombohedral GeTe in accordance with the bulk phase diagram, whereas the disordered GeTe domains still remained, consistent with the observations of transmission electron microscopy and Raman spectroscopy. Therefore, amorphousness in GeTe may be essential for the nonsegregated Ge-rich phases and the low growth temperature of the ALD enables the achievement of the structurally metastable phases.

Moisture-induced phase separation and recrystallization in amorphous solid dispersions.

PubMed

Luebbert, Christian; Sadowski, Gabriele

2017-10-30

Active Pharmaceutical Ingredients (APIs) are often dissolved in polymeric matrices to control the gastrointestinal dissolution and to stabilize the amorphous state of the API. During the pharmaceutical development of new formulations, stability studies via storage at certain temperature and relative humidity (RH) have to be carried out to verify the long-term thermodynamic stability of these formulations against unwanted recrystallization and moisture-induced amorphous-amorphous phase separation (MIAPS). This study focuses on predicting the MIAPS of API/polymer formulations at elevated RH. In a first step, the phase behavior of water-free formulations of ibuprofen (IBU) and felodipine (FEL) combined with the polymers poly(vinyl pyrrolidone) (PVP), poly(vinyl acetate) (PVAC) and poly (vinyl pyrrolidone-co-vinyl acetate) (PVPVA64) was determined experimentally by differential scanning calorimetry (DSC). The phase behavior of these water-free formulations was modeled using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). Based on this, the API solubility and MIAPS in the above-mentioned formulations at humid conditions was predicted in perfect agreement with the results of two-year lasting stability studies at 25°C/0% RH and 40°C/75% RH. MIAPS was predicted and also experimentally found for the FEL/PVP, FEL/PVPVA64 and IBU/PVP formulations, whereas MIAPS was neither predicted nor measured for the IBU/PVPVA64 system and PVAC-containing formulations. It was thus shown that the results of time-consuming long-term stability tests can be correctly predicted via thermodynamic modeling with PC-SAFT. Copyright © 2017 Elsevier B.V. All rights reserved.

The influence of co-formers on the dissolution rates of co-amorphous sulfamerazine/excipient systems.

PubMed

Gniado, Katarzyna; Löbmann, Korbinian; Rades, Thomas; Erxleben, Andrea

2016-05-17

A comprehensive study on the dissolution properties of three co-amorphous sulfamerazine/excipient systems, namely sulfamerazine/deoxycholic acid, sulfamerazine/citric acid and sulfamerazine/sodium taurocholate (SMZ/DA, SMZ/CA and SMZ/NaTC; 1:1 molar ratio), is reported. While all three co-formers stabilize the amorphous state during storage, only co-amorphization with NaTC provides a dissolution advantage over crystalline SMZ and the reasons for this were analyzed. In the case of SMZ/DA extensive gelation of DA protects the amorphous phase from crystallization upon contact with buffer, but at the same time prevents the release of SMZ into solution. Disk dissolution studies showed an improved dissolution behavior of SMZ/CA compared to crystalline SMZ. However, enhanced dissolution properties were not seen in powder dissolution testing due to poor dispersibility. Co-amorphization of SMZ and NaTC resulted in a significant increase in dissolution rate, both in powder and disk dissolution studies. Copyright © 2016. Published by Elsevier B.V.

Stability of (Fe-Tm-B) amorphous alloys: relaxation and crystallization phenomena

NASA Astrophysics Data System (ADS)

Zemčík, T.

1994-12-01

Fe-Tm-B base (TM=transition metal) amorphous alloys (metallic glasses) are thermodynamically metastable. This limits their use as otherwise favourable materials, e.g. magnetically soft, corrosion resistant and mechanically firm. By analogy of the mechanical strain-stress dependence, at a certain degree of thermal activation the amorphous structure reaches its limiting state where it changes its character and physical properties. Relaxation and early crystallization processes in amorphous alloys, starting already around 100°C, are reviewed involving subsequently stress relief, free volume shrinking, topological and chemical ordering, pre-crystallization phenomena up to partial (primary) crystallization. Two diametrically different examples are demonstrated from among the soft magnetic materials: relaxation and early crystallization processes in the Fe-Co-B metallic glasses and controlled crystallization of amorphous ribbons yielding rather modern nanocrystalline “Finemet” alloys where late relaxation and pre-crystallization phenomena overlap when forming extremely dispersive and fine-grained nanocrystals-in-amorphous-sauce structure. Mössbauer spectroscopy seems to be unique for magnetic and phase analysis of such complicated systems.

Pressure-Induced Amorphization in Single-Crystal Ta2O5 Nanowires: A Kinetic Mechanism and Improved Electrical Conductivity

NASA Astrophysics Data System (ADS)

Lu, Xujie; Hu, Qingyang; Yang, Wenge; Bai, Ligang; Sheng, Howard; Wang, Lin; Huang, Fuqiang; Wen, Jianguo; Miller, Dean; Zhao, Yusheng

2014-03-01

Pressure-induced amorphization (PIA) in single-crystal Ta2O5 nanowires is observed at 19 GPa and the obtained amorphous Ta2O5 nanowires show significant improvement in electrical conductivity. The phase transition process is unveiled by monitoring structural evolution with in-situ synchrotron XRD, PDF, Raman spectroscopy and TEM. The first principles calculations reveal the phonon modes softening during compression at particular bonds, and the analysis on the electron localization function also shows bond strength weakening at the same positions. Based on the experimental and theoretical results, a kinetic PIA mechanism is proposed and demonstrated systematically that amorphization is initiated by the disruption of connectivity between polyhedra at the particular weak-bonding positions along the a-axis in the unit cell. The one-dimensional morphology is well preserved for the pressure-induced amorphous Ta2O5 and the electrical conductivity is improved by an order of magnitude compared to traditional amorphous forms.

Mesoscale modeling of strain induced solid state amorphization in crystalline materials

NASA Astrophysics Data System (ADS)

Lei, Lei

Solid state amorphization, and in particular crystalline to amorphous transformation, can be observed in metallic alloys, semiconductors, intermetallics, minerals, and also molecular crystals when they undergo irradiation, hydrogen gas dissolution, thermal interdiffusion, mechanical alloying, or mechanical milling. Although the amorphization mechanisms may be different, the transformation occurs due to the high level of disorder introduced into the material. Milling induced solid state amorphization is proposed to be the result of accumulation of crystal defects, specifically dislocations, as the material is subjected to large deformations during the high energy process. Thus, understanding the deformation mechanisms of crystalline materials will be the first step in studying solid state amorphization in crystalline materials, which not only has scientific contributions, but also technical consequences. A phase field dislocation dynamics (PFDD) approach is employed in this work to simulate plastic deformation of molecular crystals. This PFDD model has the advantage of tracking all of the dislocations in a material simultaneously. The model takes into account the elastic interaction between dislocations, the lattice resistance to dislocation motion, and the elastic interaction of dislocations with an external stress field. The PFDD model is employed to describe the deformation of molecular crystals with pharmaceutical applications, namely, single crystal sucrose, acetaminophen, gamma-indomethacin, and aspirin. Stress-strain curves are produced that result in expected anisotropic material response due to the activation of different slip systems and yield stresses that agree well with those from experiments. The PFDD model is coupled to a phase transformation model to study the relation between plastic deformation and the solid state amorphization of crystals that undergo milling. This model predicts the amorphous volume fraction in excellent agreement with experimental observation. Finally, we incorporate the effect of stress free surfaces to model the behavior of dislocations close to these surfaces and in the presence of voids.

Electromagnetic wave absorbing properties and hyperfine interactions of Fe—Cu—Nb—Si—B nanocomposites

NASA Astrophysics Data System (ADS)

Han, Man-Gui; Guo, Wei; Wu, Yan-Hui; Liu, Min; Magundappa, L. Hadimani

2014-08-01

The Fe—Cu—Nb—Si—B alloy nanocomposite containing two ferromagnetic phases (amorphous phase and nanophase phase) is obtained by properly annealing the as-prepared alloys. High resolution transmission electron microscopy (HR-TEM) images show the coexistence of these two phases. It is found that Fe—Si nanograins are surrounded by the retained amorphous ferromagnetic phase. Mössbauer spectroscopy measurements show that the nanophase is the D03-type Fe—Si phase, which is employed to find the atomic fractions of resonant 57Fe atoms in these two phases. The microwave permittivity and permeability spectra of Fe—Cu—Nb—Si—B nanocomposite are measured in the frequency range of 0.5 GHz-10 GHz. Large relative microwave permeability values are obtained. The results show that the absorber containing the nanocomposite flakes with a volume fraction of 28.59% exhibits good microwave absorption properties. The reflection loss of the absorber is less than -10 dB in a frequency band of 1.93 GHz-3.20 GHz.

Devitrification of amorphous celecoxib.

PubMed

Gupta, Piyush; Bansal, Arvind K

2005-09-30

The purpose of this research was to analyze the devitrification of amorphous celecoxib (CEL) in the presence of different stressors (temperature, pressure, and/or humidity) encountered during processing of solid dosage forms. Amorphous CEL was prepared in situ in the analytical instruments, as well as in laboratory, by quench-cooling of melt process, and analyzed by dynamic mechanical thermal analysis, differential scanning calorimetry, microscopy, and Fourier-transform infrared spectroscopy. Amorphous CEL prepared in situ in the analytical instruments was resistant to crystallization under the influence of temperature and/or pressure, because of its protection from the external environment during preparation. These samples exhibited structural relaxation during annealing at 25 degrees C/0% relative humidity (RH) for 16 hours. Generation of amorphous CEL in the laboratory resulted in partially crystalline samples, because of exposure to environmental temperature and humidity, resulting in incomplete vitrification. Subjection to thermal stress favored crystallization of amorphous CEL into metastable polymorphic forms, which were not obtained by solvent recrystallization approach. Temperature and humidity were identified as the major factors promoting devitrification of amorphous CEL, leading to loss of solubility advantage. Exposure to International Conference on Harmonization-specified accelerated stability storage conditions (40 degrees C/75% RH) resulted in complete devitrification of amorphous CEL within 15 days. The phase-transformation process of amorphous CEL along the temperature scale was examined visually, as well as spectrally. This propensity for devitrification of amorphous CEL seemed to depend on the strength of differential molecular interactions between the amorphous and crystalline form.

Phase-change materials for non-volatile memory devices: from technological challenges to materials science issues

NASA Astrophysics Data System (ADS)

Noé, Pierre; Vallée, Christophe; Hippert, Françoise; Fillot, Frédéric; Raty, Jean-Yves

2018-01-01

Chalcogenide phase-change materials (PCMs), such as Ge-Sb-Te alloys, have shown outstanding properties, which has led to their successful use for a long time in optical memories (DVDs) and, recently, in non-volatile resistive memories. The latter, known as PCM memories or phase-change random access memories (PCRAMs), are the most promising candidates among emerging non-volatile memory (NVM) technologies to replace the current FLASH memories at CMOS technology nodes under 28 nm. Chalcogenide PCMs exhibit fast and reversible phase transformations between crystalline and amorphous states with very different transport and optical properties leading to a unique set of features for PCRAMs, such as fast programming, good cyclability, high scalability, multi-level storage capability, and good data retention. Nevertheless, PCM memory technology has to overcome several challenges to definitively invade the NVM market. In this review paper, we examine the main technological challenges that PCM memory technology must face and we illustrate how new memory architecture, innovative deposition methods, and PCM composition optimization can contribute to further improvements of this technology. In particular, we examine how to lower the programming currents and increase data retention. Scaling down PCM memories for large-scale integration means the incorporation of the PCM into more and more confined structures and raises materials science issues in order to understand interface and size effects on crystallization. Other materials science issues are related to the stability and ageing of the amorphous state of PCMs. The stability of the amorphous phase, which determines data retention in memory devices, can be increased by doping the PCM. Ageing of the amorphous phase leads to a large increase of the resistivity with time (resistance drift), which has up to now hindered the development of ultra-high multi-level storage devices. A review of the current understanding of all these issues is provided from a materials science point of view.

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.

New Cu-Free Ti-Based Composites with Residual Amorphous Matrix

PubMed Central

Nicoara, Mircea; Locovei, Cosmin; Șerban, Viorel Aurel; Parthiban, R.; Calin, Mariana; Stoica, Mihai

2016-01-01

Titanium-based bulk metallic glasses (BMGs) are considered to have potential for biomedical applications because they combine favorable mechanical properties and good biocompatibility. Copper represents the most common alloying element, which provides high amorphization capacity, but reports emphasizing cytotoxic effects of this element have risen concerns about possible effects on human health. A new copper-free alloy with atomic composition Ti42Zr10Pd14Ag26Sn8, in which Cu is completely replaced by Ag, was formulated based on Morinaga’s d-electron alloy design theory. Following this theory, the actual amount of alloying elements, which defines the values of covalent bond strength Bo and d-orbital energy Md, situates the newly designed alloy inside the BMG domain. By mean of centrifugal casting, cylindrical rods with diameters between 2 and 5 mm were fabricated from this new alloy. Differential scanning calorimetry (DSC) and X-rays diffraction (XRD), as well as microstructural analyses using optical and scanning electron microscopy (OM/SEM) revealed an interesting structure characterized by liquid phase-separated formation of crystalline Ag, as well as metastable intermetallic phases embedded in residual amorphous phases. PMID:28773455

Reaction of amorphous/crystalline SiOC/Fe interfaces by thermal annealing

DOE PAGES

Su, Qing; Zhernenkov, Mikhail; Ding, Hepeng; ...

2017-06-12

The development of revolutionary new alloys and composites is crucial to meeting materials requirements for next generation nuclear reactors. The newly developed amorphous silicon oxycarbide (SiOC) and crystalline Fe composite system has shown radiation tolerance over a wide range of temperatures. To advance understanding of this new composite, we investigate the structure and thermal stability of the interface between amorphous SiOC and crystalline Fe by combining various experimental techniques and simulation methods. We show that the SiOC/Fe interface is thermally stable up to at least 400 °C. When the annealing temperature reaches 600 °C, an intermixed region forms at thismore » interface. This region appears to be a crystalline phase that forms an incoherent interface with the Fe layer. Density functional theory (DFT) Molecular dynamics (MD) is performed on the homogeneous SiFeOC phase to study the early stages of 2 formation of the intermixed layer. Both experimental and simulation results suggest this phase has the fayalite crystal structure. As a result, the physical processes involved in the formation of the intermixed region are discussed.« less

Phase transformations induced by spherical indentation in ion-implanted amorphous silicon

NASA Astrophysics Data System (ADS)

Haberl, B.; Bradby, J. E.; Ruffell, S.; Williams, J. S.; Munroe, P.

2006-07-01

The deformation behavior of ion-implanted (unrelaxed) and annealed ion-implanted (relaxed) amorphous silicon (a-Si) under spherical indentation at room temperature has been investigated. It has been found that the mode of deformation depends critically on both the preparation of the amorphous film and the scale of the mechanical deformation. Ex situ measurements, such as Raman microspectroscopy and cross-sectional transmission electron microscopy, as well as in situ electrical measurements reveal the occurrence of phase transformations in all relaxed a-Si films. The preferred deformation mode of unrelaxed a-Si is plastic flow, only under certain high load conditions can this state of a-Si be forced to transform. In situ electrical measurements have revealed more detail of the transformation process during both loading and unloading. We have used ELASTICA simulations to obtain estimates of the depth of the metallic phase as a function of load, and good agreement is found with the experiment. On unloading, a clear change in electrical conductivity is observed to correlate with a "pop-out" event on load versus penetration curves.

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.

Crystallized and amorphous vortices in rotating atomic-molecular Bose-Einstein condensates

PubMed Central

Liu, Chao-Fei; Fan, Heng; Gou, Shih-Chuan; Liu, Wu-Ming

2014-01-01

Vortex is a topological defect with a quantized winding number of the phase in superfluids and superconductors. Here, we investigate the crystallized (triangular, square, honeycomb) and amorphous vortices in rotating atomic-molecular Bose-Einstein condensates (BECs) by using the damped projected Gross-Pitaevskii equation. The amorphous vortices are the result of the considerable deviation induced by the interaction of atomic-molecular vortices. By changing the atom-molecule interaction from attractive to repulsive, the configuration of vortices can change from an overlapped atomic-molecular vortices to carbon-dioxide-type ones, then to atomic vortices with interstitial molecular vortices, and finally into independent separated ones. The Raman detuning can tune the ratio of the atomic vortex to the molecular vortex. We provide a phase diagram of vortices in rotating atomic-molecular BECs as a function of Raman detuning and the strength of atom-molecule interaction. PMID:24573303

Electron microscopy study of Ni induced crystallization in amorphous Si thin films

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

Radnóczi, G. Z.; Battistig, G.; Pécz, B., E-mail: pecz.bela@ttk.mta.hu

2015-02-17

The crystallization of amorphous silicon is studied by transmission electron microscopy. The effect of Ni on the crystallization is studied in a wide temperature range heating thinned samples in-situ inside the microscope. Two cases of limited Ni source and unlimited Ni source are studied and compared. NiSi{sub 2} phase started to form at a temperature as low as 250°C in the limited Ni source case. In-situ observation gives a clear view on the crystallization of silicon through small NiSi{sub 2} grain formation. The same phase is observed at the crystallization front in the unlimited Ni source case, where a secondmore » region is also observed with large grains of Ni{sub 3}Si{sub 2}. Low temperature experiments show, that long annealing of amorphous silicon at 410 °C already results in large crystallized Si regions due to the Ni induced crystallization.« less

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

DeVol, Ross T.; Sun, Chang-Yu; Marcus, Matthew A.

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO 3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive. They were inferred from non-nacre-forming larval shells, or from a residue of amorphous material surrounding mature gastropod nacre tablets, and have only once been observed in bivalve nacre. Here we present the first direct observation of ACC precursors to nacre formation, obtained from the growth front of nacre in gastropodmore » shells from red abalone (Haliotis rufescens), using synchrotron spectromicroscopy. Surprisingly, the abalone nacre data show the same ACC phases that are precursors to calcite (CaCO 3) formation in sea urchin spicules, and not proto-aragonite or poorly crystalline aragonite (pAra), as expected for aragonitic nacre. In contrast, we find pAra in coral.« less

Aqueous sodium chloride induced intergranular corrosion of Al-Li-Cu alloys

NASA Technical Reports Server (NTRS)

Pizzo, P. P.; Daeschner, D. L.

1986-01-01

Two methods have been explored to assess the susceptibility of Al-Li-Cu alloys to intergranular corrosion in aqueous sodium chloride solution. They are: (1) constant extension rate testing with and without alternate-immersion preexposure and (2) metallographic examination after exposure to a NaCl-H2O2 corrosive solution per Mil-H-6088F. Intergranular corrosion was found to occur in both powder and ingot metallurgy alloys of similar composition, using both methods. Underaging rendered the alloys most susceptible. The results correlate to stress-corrosion data generated in conventional time-to-failure and crack growth-rate tests. Alternate-immersion preexposure may be a reliable means to assess stress corrosion susceptibility of Al-Li-Cu alloys.

In Situ TEM Nanoindentation Studies on Stress-Induced Phase Transformations in Metallic Materials

DOE PAGES

Liu, Y.; Wang, H.; Zhang, X.

2015-11-30

Though abundant phase transformations are in general thermally driven processes, there are many examples wherein stresses can induce phase transformations. We applied numerous in situ techniques, such as in situ x-ray diffraction and neutron diffraction in order to reveal phase transformations. Recently, an in situ nanoindentation technique coupled with transmission electron microscopy demonstrated the capability to directly correlating stresses with phase transformations and microstructural evolutions at a submicron length scale. We briefly review in situ studies on stress-induced diffusional and diffusionless phase transformations in amorphous CuZrAl alloy and NiFeGa shape memory alloy. Moreover, in the amorphous CuZrAl, in situ nanoindentationmore » studies show that the nucleation of nanocrystals (a diffusional process) occurs at ultra-low stresses manifested by a prominent stress drop. In the NiFeGa shape memory alloy, two distinctive types of martensitic (diffusionless) phase transformations accompanied by stress plateaus are observed, including a reversible gradual phase transformation at low stress levels, and an irreversible abrupt phase transition at higher stress levels.« less

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

PubMed

Smith, Rodney D L; Prévot, Mathieu S; Fagan, Randal D; Zhang, Zhipan; Sedach, Pavel A; Siu, Man Kit Jack; Trudel, Simon; Berlinguette, Curtis P

2013-04-05

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Large-Scale Structure and Hyperuniformity of Amorphous Ices

NASA Astrophysics Data System (ADS)

Martelli, Fausto; Torquato, Salvatore; Giovambattista, Nicolas; Car, Roberto

2017-09-01

We investigate the large-scale structure of amorphous ices and transitions between their different forms by quantifying their large-scale density fluctuations. Specifically, we simulate the isothermal compression of low-density amorphous ice (LDA) and hexagonal ice to produce high-density amorphous ice (HDA). Both HDA and LDA are nearly hyperuniform; i.e., they are characterized by an anomalous suppression of large-scale density fluctuations. By contrast, in correspondence with the nonequilibrium phase transitions to HDA, the presence of structural heterogeneities strongly suppresses the hyperuniformity and the system becomes hyposurficial (devoid of "surface-area fluctuations"). Our investigation challenges the largely accepted "frozen-liquid" picture, which views glasses as structurally arrested liquids. Beyond implications for water, our findings enrich our understanding of pressure-induced structural transformations in glasses.

Predict the glass transition temperature and plasticization of β-cyclodextrin/water binary system by molecular dynamics simulation.

PubMed

Zhou, Guohui; Zhao, Tianhai; Wan, Jie; Liu, Chengmei; Liu, Wei; Wang, Risi

2015-01-12

The glass transition temperature, diffusion behavior and plasticization of β-cyclodextrin (β-CD), and three amorphous β-CD/water mixtures (3%, 5% and 10% [w/w] water, respectively) were investigated by molecular dynamics simulation, which were performed using Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field and isothermal-isobaric ensembles. The specific volumes of four amorphous cells were obtained as a function of temperature. The glass transition temperatures (T(g)) were estimated to be 334.25 K, 325.12 K, 317.32 K, and 305.41 K for amorphous β-CD containing 0%, 3%, 5% and 10% w/w water, respectively, which compares well with the values observed in published literature. The radial distribution function was computed to elucidate the intermolecular interactions between amorphous β-CD and water, which acts as a plasticizer. These results indicate that the hydrogen bond interactions of oxygen in hydroxyl ions was higher than oxygen in acetal groups in β-CD amorphous mixtures with that in water, due to less accessibility of ring oxygens to the surrounding water molecules. The mobility of water molecules was investigated over various temperature ranges, including the rubbery and glassy phases of the β-CD/water mixtures, by calculating the diffusion coefficients and the fractional free volume. In β-CD amorphous models, the higher mobility of water molecules was observed at temperatures above Tg, and almost no change was observed at temperatures below T(g). Copyright © 2014 Elsevier Ltd. All rights reserved.

Crystal plasticity modeling of β phase deformation in Ti-6Al-4V

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

Moore, John A.; Barton, Nathan R.; Florando, Jeff

Ti-6Al-4V is an alloy of titanium that dominates titanium usage in applications ranging from mass-produced consumer goods to high-end aerospace parts. The material's structure on a microscale is known to affect its mechanical properties but these effects are not fully understood. Specifically, this work will address the effects of low volume fraction intergranular β phase on Ti-6Al-4V's mechanical response during the transition from elastic to plastic deformation. A crystal plasticity-based finite element model is used to fully resolve the deformation of the β phase for the first time. This high fidelity model captures mechanisms difficult to access via experiments ormore » lower fidelity models. Lastly, the results are used to assess lower fidelity modeling assumptions and identify phenomena that have ramifications for failure of the material.« less

Crystal plasticity modeling of β phase deformation in Ti-6Al-4V

DOE PAGES

Moore, John A.; Barton, Nathan R.; Florando, Jeff; ...

2017-08-24

Ti-6Al-4V is an alloy of titanium that dominates titanium usage in applications ranging from mass-produced consumer goods to high-end aerospace parts. The material's structure on a microscale is known to affect its mechanical properties but these effects are not fully understood. Specifically, this work will address the effects of low volume fraction intergranular β phase on Ti-6Al-4V's mechanical response during the transition from elastic to plastic deformation. A crystal plasticity-based finite element model is used to fully resolve the deformation of the β phase for the first time. This high fidelity model captures mechanisms difficult to access via experiments ormore » lower fidelity models. Lastly, the results are used to assess lower fidelity modeling assumptions and identify phenomena that have ramifications for failure of the material.« less

The degree and nature of radiation damage in zircon observed by 29Si nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Farnan, I.; Salje, E. K. H.

2001-02-01

A quantitative analysis of 29Si nuclear magnetic resonance spectra of radiation damaged, natural zircons showed that the local structure in crystalline and amorphous regions depend explicitly on radiation dose. Nonpercolating amorphous islands of high density "glass" within the crystalline matrix show a low interconnectivity of SiO4 tetrahedra. This structural state is quite different from that of the high dose, percolating regions of low density glass with more polymerised tetrahedra. A continuous nonlinear dose dependence between the high and low density glass states is reported. A continuous evolution of the local structure of the crystalline phase up to the percolation point is also reported. No phase separation into binary oxides was observed. The total number of permanently displaced atoms per α-recoil event is ˜3800 atoms for low radiation doses and decreases to ˜2000 atoms for 10×1018 α events/g. No indication of partitioning of paramagnetic impurities between crystalline and amorphous regions was found for these natural zircons. The amorphous fractions of the metamict zircons were determined as a function of their accumulated radiation dose. These values coincide closely with those recently determined by x-ray diffraction studies. They are much greater than previously assumed based on density measurements. The dose dependence is consistent with the concept of direct impact amorphization in the atomic cascade following an α-recoil event.

Phase Evaluation in Al2O3 Fiber-Reinforced Ti2AlC During Sintering in the 1300 degrees C-1500 degrees C Temperature Range

DTIC Science & Technology

2011-01-01

composition: 97% Al2O3 and 3% SiO2] fibers. In both cases, the fibers were chopped with a razor blade into 5 cm lengths. Mixing of the powder and...the presence of XRD amorphous Ti- aluminides (see below) or other phases cannot be ruled out at this juncture. When the XRD spectrum of the as-received...not shown). No peaks belonging to any Ti- aluminide were found suggesting them to be amorphous or at most nano-crystalline. A typical TEM micrograph of

Blends of POSS-PEO(n=4)(8) and high molecular weight poly(ethylene oxide) as solid polymer electrolytes for lithium batteries.

PubMed

Zhang, Hanjun; Kulkarni, Sunil; Wunder, Stephanie L

2007-04-12

Solid polymer electrolyte blends were prepared with POSS-PEO(n=4)8 (3K), poly(ethylene oxide) (PEO(600K)), and LiClO4 at different salt concentrations (O/Li = 8/1, 12/1, and 16/1). POSS-PEO(n=4)8/LiClO4 is amorphous at all O/Li investigated, whereas PEO(600K) is amorphous only for O/Li = 8/1 and semicrystalline for O/Li = 12/1 and 16/1. The tendency of PEO(600K) to crystallize limited the amount of POSS-PEO(n=4)(8) that could be incorporated into the blends, so that the greatest incorporation of POSS-PEO(n=4)(8) occurred for O/Li = 8/1. Blends of POSS-PEO(n=4)(8)/PEO(600K)/LiClO4 (O/Li = 8/1 and 12/1) microphase separated into two amorphous phases, a low T(g) phase of composition 85% POSS-PEO(n=4)(8)/15% PEO(600K) and a high T(g) phase of composition 29% POSS-PEO(n=4)(8)/71% PEO(600K). For O/Li = 16/1, the blends contained crystalline (pure PEO(600K)), and two amorphous phases, one rich in POSS-PEO(n=4)(8) and one rich in PEO(600K). Microphase, rather than macrophase separation was believed to occur as a result of Li(+)/ether oxygen cross-link sites. The conductivity of the blends depended on their composition. As expected, crystallinity decreased the conductivity of the blends. For the amorphous blends, when the low T(g) (80/20) phase was the continuous phase, the conductivity was intermediate between that of pure PEO(600K) and POSS-PEO(n=4)(8). When the high T(g) (70/30, 50/50, 30/70, and 20/80) phase was the continuous phase, the conductivity of the blend and PEO(600K) were identical, and lower than that for the POSS-PEO(n=4)(8) over the whole temperature range (10-90 degrees C). This suggests that the motions of the POSS-PEO(n=4)(8) were slowed down by the dynamics of the long chain PEO(600K) and that the minor, low Tg phase was not interconnected and thus did not contribute to enhanced conductivity. At temperatures above T(m) of PEO(600K), addition of the POSS-PEO(n=4)(8) did not result in conductivity improvement. The highest RT conductivity, 8 x 10(-6) S/cm, was obtained for a 60% POSS-PEO(n=4)(8)/40% PEO(600K)/LiClO4 (O/Li = 12/1) blend.

Bi12TiO20 crystallization in a Bi2O3-TiO2-SiO2-Nd2O3 system

NASA Astrophysics Data System (ADS)

Slavov, S.; Jiao, Z.

2018-03-01

Polycrystalline mono-phase bismuth titanate was produced by free cooling from melts heated to 1170 °C. The control over the initial amounts in the starting compositions in the system Bi2O3/TiO2/SiO2/Nd2O3 and over the thermal gradient of the heat process resulted in the formation of specific structures and microstructures of monophase sillenite ceramics. The main phase Bi12TiO20 belongs to the amorphous network groups based on oxides of silicon, bismuth and titanium. In this work, we demonstrated a way to control the crystalline and amorphous phase formation in bulk poly-crystalline materials in the selected system.

Using Environment-Sensitive Fluorescent Probes to Characterize Liquid-Liquid Phase Separation in Supersaturated Solutions of Poorly Water Soluble Compounds.

PubMed

Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2015-11-01

Highly supersaturated aqueous solutions of poorly soluble compounds can undergo liquid-liquid phase separation (LLPS) when the concentration exceeds the "amorphous solubility". This phenomenon has been widely observed during high throughput screening of new molecular entities as well as during the dissolution of amorphous solid dispersions. In this study, we have evaluated the use of environment-sensitive fluorescence probes to investigate the formation and properties of the non-crystalline drug-rich aggregates formed in aqueous solutions as a result of LLPS. Six different environment-sensitive fluorophores were employed to study LLPS in highly supersaturated solutions of several model compounds, all dihydropyridine derivatives. Each fluoroprobe exhibited a large hypsochromic shift with decreasing environment polarity. Upon drug aggregate formation, the probes partitioned into the drug-rich phase and exhibited changes in emission wavelength and intensity consistent with sensing a lower polarity environment. The LLPS onset concentrations determined using the fluorescence measurements were in good agreement with light scattering measurements as well as theoretically estimated amorphous solubility values. Environment-sensitive fluorescence probes are useful to help understand the phase behavior of highly supersaturated aqueous solutions, which in turn is important in the context of developing enabling formulations for poorly soluble compounds.

Microstructure and magnetic behavior of Mn doped GeTe chalcogenide semiconductors based phase change materials

NASA Astrophysics Data System (ADS)

Adam, Adam Abdalla Elbashir; Cheng, Xiaomin; Abuelhassan, Hassan H.; Miao, Xiang Shui

2017-06-01

Phase-change materials (PCMs) are the most promising candidates to be used as an active media in the universal data storage and spintronic devices, due to their large differences in physical properties of the amorphous-crystalline phase transition behavior. In the present study, the microstructure, magnetic and electrical behaviors of Ge0.94Mn0.06Te thin film were investigated. The crystallographic structure of Ge0.94Mn0.06Te thin film was studied sing X-ray diffractometer (XRD) and High Resolution Transmission Electron Microscope (HR-TEM). The XRD pattern showed that the crystallization structure of the film was rhombohedral phase for GeTe with a preference (202) orientation. The HR-TEM image of the crystalline Ge0.94Mn0.06Te thin film demonstrated that, there were two large crystallites and small amorphous areas. The magnetization as a function of the magnetic field analyses of both amorphous and crystalline states showed the ferromagnetic hysteretic behaviors. Then, the hole carriers concentration of the film was measured and it found to be greater than 1021 cm-3 at room temperature. Moreover, the anomalous of Hall Effect (AHE) was clearly observed for the measuring temperatures 5, 10 and 50 K. The results demonstrated that the magnitude of AHE decreased when the temperature was increasing.

Direct Observation of the Thickness-Induced Crystallization and Stress Build-Up during Sputter-Deposition of Nanoscale Silicide Films.

PubMed

Krause, Bärbel; Abadias, Gregory; Michel, Anny; Wochner, Peter; Ibrahimkutty, Shyjumon; Baumbach, Tilo

2016-12-21

The kinetics of phase transitions during formation of small-scale systems are essential for many applications. However, their experimental observation remains challenging, making it difficult to elucidate the underlying fundamental mechanisms. Here, we combine in situ and real-time synchrotron X-ray diffraction (XRD) and X-ray reflectivity (XRR) experiments with substrate curvature measurements during deposition of nanoscale Mo and Mo 1-x Si x films on amorphous Si (a-Si). The simultaneous measurements provide direct evidence of a spontaneous, thickness-dependent amorphous-to-crystalline (a-c) phase transition, associated with tensile stress build-up and surface roughening. This phase transformation is thermodynamically driven, the metastable amorphous layer being initially stabilized by the contributions of surface and interface energies. A quantitative analysis of the XRD data, complemented by simulations of the transformation kinetics, unveils an interface-controlled crystallization process. This a-c phase transition is also dominating the stress evolution. While stress build-up can significantly limit the performance of devices based on nanostructures and thin films, it can also trigger the formation of these structures. The simultaneous in situ access to the stress signal itself, and to its microstructural origins during structure formation, opens new design routes for tailoring nanoscale devices.

Experimental Investigation on Laser Impact Welding of Fe-Based Amorphous Alloys to Crystalline Copper

PubMed Central

Wang, Xiao; Luo, Yapeng; Huang, Tao; Liu, Huixia

2017-01-01

Recently, amorphous alloys have attracted many researchers’ attention for amorphous structures and excellent properties. However, the welding of amorphous alloys to traditional metals in the microscale is not easy to realize in the process with amorphous structures unchanged, which restrains the application in industry. In this paper, a new method of welding Fe-based amorphous alloys (GB1K101) to crystalline copper by laser impact welding (LIW) is investigated. A series of experiments was conducted under different laser energies, during which Fe-based amorphous alloys and crystalline copper were welded successfully by LIW. In addition, the microstructure and mechanical properties of welding joints were observed and measured, respectively. The results showed that the surface wave and springback were observed on the flyer plate after LIW. The welding interface was straight or wavy due to different plastic deformation under different laser energies. The welding interface was directly bonded tightly without visible defects. No visible element diffusion and intermetallic phases were found in the welding interface. The Fe-based amorphous alloys retained amorphous structures after LIW under the laser energy of 835 mJ. The nanoindentation hardness across the welding interface showed an increase on both sides of the welding interface. The results of the lap shearing test showed that the fracture position was on the side of copper coil. PMID:28772886

From amorphous to nanocrystalline: the effect of nanograins in amorphous matrix on the thermal conductivity of hot-wire chemical-vapor deposited silicon films

DOE PAGES

Kearney, B. T.; Jugdersuren, B.; Queen, D. R.; ...

2017-12-28

Here, we have measured the thermal conductivity of amorphous and nanocrystalline silicon films with varying crystalline content from 85K to room temperature. The films were prepared by the hot-wire chemical-vapor deposition, where the crystalline volume fraction is determined by the hydrogen (H2) dilution ratio to the processing silane gas (SiH4), R=H2/SiH4. We varied R from 1 to 10, where the films transform from amorphous for R < 3 to mostly nanocrystalline for larger R. Structural analyses show that the nanograins, averaging from 2 to 9nm in sizes with increasing R, are dispersed in the amorphous matrix. The crystalline volume fractionmore » increases from 0 to 65% as R increases from 1 to 10. The thermal conductivities of the two amorphous silicon films are similar and consistent with the most previous reports with thicknesses no larger than a few um deposited by a variety of techniques. The thermal conductivities of the three nanocrystalline silicon films are also similar, but are about 50-70% higher than those of their amorphous counterparts. The heat conduction in nanocrystalline silicon films can be understood as the combined contribution in both amorphous and nanocrystalline phases, where increased conduction through improved nanocrystalline percolation path outweighs increased interface scattering between silicon nanocrystals and the amorphous matrix.« less

Experimental Investigation on Laser Impact Welding of Fe-Based Amorphous Alloys to Crystalline Copper.

PubMed

Wang, Xiao; Luo, Yapeng; Huang, Tao; Liu, Huixia

2017-05-12

Recently, amorphous alloys have attracted many researchers' attention for amorphous structures and excellent properties. However, the welding of amorphous alloys to traditional metals in the microscale is not easy to realize in the process with amorphous structures unchanged, which restrains the application in industry. In this paper, a new method of welding Fe-based amorphous alloys (GB1K101) to crystalline copper by laser impact welding (LIW) is investigated. A series of experiments was conducted under different laser energies, during which Fe-based amorphous alloys and crystalline copper were welded successfully by LIW. In addition, the microstructure and mechanical properties of welding joints were observed and measured, respectively. The results showed that the surface wave and springback were observed on the flyer plate after LIW. The welding interface was straight or wavy due to different plastic deformation under different laser energies. The welding interface was directly bonded tightly without visible defects. No visible element diffusion and intermetallic phases were found in the welding interface. The Fe-based amorphous alloys retained amorphous structures after LIW under the laser energy of 835 mJ. The nanoindentation hardness across the welding interface showed an increase on both sides of the welding interface. The results of the lap shearing test showed that the fracture position was on the side of copper coil.

From amorphous to nanocrystalline: the effect of nanograins in amorphous matrix on the thermal conductivity of hot-wire chemical-vapor deposited silicon films

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

Kearney, B. T.; Jugdersuren, B.; Queen, D. R.

Here, we have measured the thermal conductivity of amorphous and nanocrystalline silicon films with varying crystalline content from 85K to room temperature. The films were prepared by the hot-wire chemical-vapor deposition, where the crystalline volume fraction is determined by the hydrogen (H2) dilution ratio to the processing silane gas (SiH4), R=H2/SiH4. We varied R from 1 to 10, where the films transform from amorphous for R < 3 to mostly nanocrystalline for larger R. Structural analyses show that the nanograins, averaging from 2 to 9nm in sizes with increasing R, are dispersed in the amorphous matrix. The crystalline volume fractionmore » increases from 0 to 65% as R increases from 1 to 10. The thermal conductivities of the two amorphous silicon films are similar and consistent with the most previous reports with thicknesses no larger than a few um deposited by a variety of techniques. The thermal conductivities of the three nanocrystalline silicon films are also similar, but are about 50-70% higher than those of their amorphous counterparts. The heat conduction in nanocrystalline silicon films can be understood as the combined contribution in both amorphous and nanocrystalline phases, where increased conduction through improved nanocrystalline percolation path outweighs increased interface scattering between silicon nanocrystals and the amorphous matrix.« less

A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling.

PubMed

Baxter, Emma F; Bennett, Thomas D; Cairns, Andrew B; Brownbill, Nick J; Goodwin, Andrew L; Keen, David A; Chater, Philip A; Blanc, Frédéric; Cheetham, Anthony K

2016-03-14

X-ray diffraction has been used to investigate the kinetics of amorphization through ball-milling at 20 Hz, for five zeolitic imidazolate frameworks (ZIFs) - ZIF-8, ZIF-4, ZIF-zni, BIF-1-Li and CdIF-1. We find that the rates of amorphization for the zinc-containing ZIFs increase with increasing solvent accessible volume (SAV) in the sequence ZIF-8 > ZIF-4 > ZIF-zni. The Li-B analogue of the dense ZIF-zni amorphizes more slowly than the corresponding zinc phase, with the behaviour showing a correlation with their relative bulk moduli and SAVs. The cadmium analogue of ZIF-8 (CdIF-1) amorphizes more rapidly than the zinc counterpart, which we ascribe primarily to its relatively weak M-N bonds as well as the higher SAV. The results for the ZIFs are compared to three classical zeolites - Na-X, Na-Y and ZSM-5 - with these taking up to four times longer to amorphize. The presence of adsorbed solvent in the pores is found to render both ZIF and zeolite frameworks more resistant to amorphization. X-ray total scattering measurements show that amorphous ZIF-zni is structurally indistinguishable from amorphous ZIF-4 with both structures retaining the same short-range order that is present in their crystalline precursors. By contrast, both X-ray total scattering measurements and (113)Cd NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor.