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.

Band gap tuning of amorphous Al oxides by Zr alloying

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

Canulescu, S., E-mail: stec@fotonik.dtu.dk; Schou, J.; Jones, N. C.

2016-08-29

The optical band gap and electronic structure of amorphous Al-Zr mixed oxides with Zr content ranging from 4.8 to 21.9% were determined using vacuum ultraviolet and X-ray absorption spectroscopy. The light scattering by the nano-porous structure of alumina at low wavelengths was estimated based on the Mie scattering theory. The dependence of the optical band gap of the Al-Zr mixed oxides on the Zr content deviates from linearity and decreases from 7.3 eV for pure anodized Al{sub 2}O{sub 3} to 6.45 eV for Al-Zr mixed oxides with a Zr content of 21.9%. With increasing Zr content, the conduction band minimum changes non-linearlymore » as well. Fitting of the energy band gap values resulted in a bowing parameter of ∼2 eV. The band gap bowing of the mixed oxides is assigned to the presence of the Zr d-electron states localized below the conduction band minimum of anodized Al{sub 2}O{sub 3}.« less

Temperature-Dependent Helium Ion-Beam Mixing in an Amorphous SiOC/Crystalline Fe Composite

DOE PAGES

Su, Qing; Price, Lloyd; Shao, Lin; ...

2016-10-31

Temperature dependent He-irradiation-induced ion-beam mixing between amorphous silicon oxycarbide (SiOC) and crystalline Fe was examined with a transmission electron microscope (TEM) and via Rutherford backscattering spectrometry (RBS). The Fe marker layer (7.2 ± 0.8 nm) was placed in between two amorphous SiOC layers (200 nm). The amount of ion-beam mixing after 298, 473, 673, 873, and 1073 K irradiation was investigated. Both TEM and RBS results showed no ion-beam mixing between Fe and SiOC after 473 and 673 K irradiation and a very trivial amount of ion-beam mixing (~2 nm) after 298 K irradiation. At irradiation temperatures higher than 873more » K, the Fe marker layer broke down and RBS could no longer be used to quantitatively examine the amount of ion mixing. The results indicate that the Fe/SiOC nanocomposite is thermally stable and tends to demix in the temperature range from 473 to 673 K. For application of this composite structure at temperatures of 873 K or higher, layer stability is a key consideration.« less

Midinfrared wavelength conversion in hydrogenated amorphous silicon waveguides

NASA Astrophysics Data System (ADS)

Wang, Jiang; Wang, Zhaolu; Huang, Nan; Han, Jing; Li, Yongfang; Liu, Hongjun

2017-10-01

Midinfrared (MIR) wavelength conversion based on degenerate four-wave mixing is theoretically investigated in hydrogenated amorphous silicon (a-Si:H) waveguides. The broadband phase mismatch is achieved in the normal group-velocity dispersion regime. The conversion bandwidth is extended to 900 nm, and conversion efficiency of up to -14 dB with a pump power of 70 mW in a 2-mm long a-Si:H rib waveguides is obtained. This low-power on-chip wavelength converter will have potential for application in a wide range of MIR nonlinear optic devices.

The mixing mechanism during lithiation of Si negative electrode in Li-ion batteries: an ab initio molecular dynamics study.

PubMed

Johari, Priya; Qi, Yue; Shenoy, Vivek B

2011-12-14

In order to realize Si as a negative electrode material in commercial Li-ion batteries, it is important to understand the mixing mechanism of Li and Si, and stress evolution during lithiation in Si negative electrode of Li-ion batteries. Available experiments mainly provide the diffusivity of Li in Si as an averaged property, neglecting information regarding diffusivity of Si. However, if Si can diffuse as fast as Li, the stress generated during Li diffusion can be reduced. We, therefore, studied the diffusivity of Li as well as Si atoms in the Si-anode of Li-ion battery using an ab initio molecular dynamics-based methodology. The electrochemical insertion of Li into crystalline Si prompts a crystalline-to-amorphous phase transition. We considered this situation and thus examined the diffusion kinetics of Li and Si atoms in both crystalline and amorphous Si. We find that Li diffuses faster in amorphous Si as compared to crystalline Si, while Si remains relatively immobile in both cases and generates stresses during lithiation. To further understand the mixing mechanism and to relate the structure with electrochemical mixing, we analyzed the evolution of the structure during lithiation and studied the mechanism of breaking of Si-Si network by Li. We find that Li atoms break the Si rings and chains and create ephemeral structures such as stars and boomerangs, which eventually transform to Si-Si dumbbells and isolated Si atoms in the LiSi phase. Our results are found to be in agreement with the available experimental data and provide insights into the mixing mechanism of Li and Si in Si negative electrode of Li-ion batteries.

Barrier coated drug layered particles for enhanced performance of amorphous solid dispersion dosage form.

PubMed

Puri, Vibha; Dantuluri, Ajay K; Bansal, Arvind K

2012-01-01

Amorphous solid dispersions (ASDs) may entail tailor-made dosage form design to exploit their solubility advantage. Surface phenomena dominated the performance of amorphous celecoxib solid dispersion (ACSD) comprising of amorphous celecoxib (A-CLB), polyvinylpyrrolidone, and meglumine (7:2:1, w/w). ACSD cohesive interfacial interactions hindered its capsule dosage form dissolution (Puri V, Dhantuluri AK, Bansal AK 2011. J Pharm Sci 100:2460-2468). Furthermore, ACSD underwent significant devitrification under environmental stress. In the present study, enthalpy relaxation studies revealed its free surface to contribute to molecular mobility. Based on all these observations, barrier coated amorphous CLB solid dispersion layered particles (ADLP) were developed by Wurster process, using microcrystalline cellulose as substrate and polyvinyl alcohol (PVA), inulin, and polyvinyl acetate phthalate (PVAP) as coating excipients. Capsule formulations of barrier coated-ADLP could achieve rapid dispersibility and high drug release. Evaluation under varying temperature and RH conditions suggested the crystallization inhibitory efficiency in order of inulin < PVA ≈ PVAP; however, under only temperature treatment, crystallization inhibition increased with increase in T(g) of the coating material. Simulated studies using DSC evidenced drug-polymer mixing at the interface as a potential mechanism for surface stabilization. In conclusion, surface modification yielded a fast dispersing robust high drug load ASD based dosage form. Copyright © 2011 Wiley-Liss, Inc.

Amorphous Silk Fibroin Membranes for Separation of CO2

NASA Technical Reports Server (NTRS)

Aberg, Christopher M.; Patel, Anand K.; Gil, Eun Seok; Spontak, Richard J.; Hagg, May-Britt

2009-01-01

Amorphous silk fibroin has shown promise as a polymeric material derivable from natural sources for making membranes for use in removing CO2 from mixed-gas streams. For most applications of silk fibroin, for purposes other than gas separation, this material is used in its highly crystalline, nearly natural form because this form has uncommonly high tensile strength. However, the crystalline phase of silk fibroin is impermeable, making it necessary to convert the material to amorphous form to obtain the high permeability needed for gas separation. Accordingly, one aspect of the present development is a process for generating amorphous silk fibroin by treating native silk fibroin in an aqueous methanol/salt solution. The resulting material remains self-standing and can be prepared as thin film suitable for permeation testing. The permeability of this material by pure CO2 has been found to be highly improved, and its mixed-gas permeability has been found to exceed the mixed-gas permeabilities of several ultrahigh-CO2-permeable synthetic polymers. Only one of the synthetic polymers poly(trimethylsilylpropyne) [PTMSP] may be more highly permeable by CO2. PTMSP becomes unstable with time, whereas amorphous silk should not, although at the time of this reporting this has not been conclusively proven.

Influence of Synthesis Mode of Supplement Based on Calcium Hydrosylicates on the Structure and Properties of Lime Compositions

NASA Astrophysics Data System (ADS)

Loganina, V. I.; Pyshkina, I. S.

2017-11-01

It was proposed to use synthesized calcium hydrosilicates in finishing lime dry mixes as a modifying supplement. The effect of substances containing amorphous silica which are used for synthesis on the activity of the modifying supplement was established. The effect of the synthesis mode of supplement on the structure formation of lime compositions was illustrated. It was found that the injection of supplements of hydrosilicates accelerates the increase of mechanical strength. The efficiency of the modifying supplements of amorphous silica, such as diatomite, in the synthesis was shown.

Magnetron-Sputtered Amorphous Metallic Coatings

NASA Technical Reports Server (NTRS)

Thakoor, A. P.; Mehra, M.; Khanna, S. K.

1985-01-01

Amorphous coatings of refractory metal/metalloid-based alloys deposited by magnetron sputtering provide extraordinary hardness and wear resistance. Sputtering target fabricated by thoroughly mixing powders of tungsten, rhenium, and boron in stated proportions and pressing at 1,200 degrees C and 3,000 lb/in. to second power (21 MPa). Substrate lightly etched by sputtering before deposition, then maintained at bias of - 500 V during initial stages of film growth while target material sputtered onto it. Argon gas at pressure used as carrier gas for sputter deposition. Coatings dense, pinhole-free, extremely smooth, and significantly resistant to chemical corrosion in acidic and neutral aqueous environments.

Why is it so difficult to classify Renazzo-type (CR) carbonaceous chondrites? - Implications from TEM observations of matrices for the sequences of aqueous alteration

NASA Astrophysics Data System (ADS)

Abreu, Neyda M.

2016-12-01

A number of different classifications have been proposed for the CR chondrites; this study aims at reconciling these different schemes. Mineralogy-based classification has proved particularly challenging for weakly to moderately altered CRs because incipient mineral replacement and elemental mobilization arising from aqueous alteration only affected the most susceptible primary phases, which are generally located in the matrix. Secondary matrix phases are extremely fine-grained (generally sub-micron) and heterogeneously mixed with primary nebular materials. Compositional and isotopic classification parameters are fraught with confounding factors, such as terrestrial weathering, impact processes, and variable abundance of clasts from different regions of the CR parent body or from altogether different planetary bodies. Here, detailed TEM observations from eighteen FIB sections retrieved from the matrices of nine Antarctic CR chondrites (EET 96259, GRA 95229, GRO 95577, GRO 03116, LAP 02342, LAP 04516, LAP 04720, MIL 07525, and MIL 090001) are presented, representing a range of petrologic types. Amorphous Fe-Mg silicates are found to be the dominant phase in all but the most altered CR chondrite matrices, which still retain significant amounts of these amorphous materials. Amorphous Fe-Mg silicates are mixed with phyllosilicates at the nanometer scale. The ratio of amorphous Fe-Mg silicates to phyllosilicates decreases as: (1) the size of phyllosilicates, (2) abundance of magnetite, and (3) replacement of Fe-Ni sulfides increase. Carbonates are only abundant in the most altered CR chondrite, GRO 95577. Nanophase Fe-Ni metal and tochilinite are present small abundances in most CR matrices. Based on the presence, abundance and size of phyllosilicates with respect to amorphous Fe-Mg silicates, the sub-micron features of CR chondrites have been linked to existing classification sequences, and possible reasons for inconsistencies among classification schemes are discussed.

Determine the permeability of an amorphous mixture of polydimethylsiloxane and dealuminated zeolite ZSM-5 to various ethanol-water solutions using molecular simulations.

EPA Science Inventory

An amorphous mixture of PDMS and multi-cellular fragments of ZSM-5 is brought together to approximate the properties of a mixed matrix membrane of PDMS with ZSM-5. The permeability coefficient of the amorphous mixture for pure water is the product of the diffusion coefficient of...

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.

Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

PubMed

Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

2014-11-18

Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

Construction of drug-polymer thermodynamic phase diagrams using Flory-Huggins interaction theory: identifying the relevance of temperature and drug weight fraction to phase separation within solid dispersions.

PubMed

Tian, Yiwei; Booth, Jonathan; Meehan, Elizabeth; Jones, David S; Li, Shu; Andrews, Gavin P

2013-01-07

Amorphous drug-polymer solid dispersions have the potential to enhance the dissolution performance and thus bioavailability of BCS class II drug compounds. The principle drawback of this approach is the limited physical stability of amorphous drug within the dispersion. Accurate determination of the solubility and miscibility of drug in the polymer matrix is the key to the successful design and development of such systems. In this paper, we propose a novel method, based on Flory-Huggins theory, to predict and compare the solubility and miscibility of drug in polymeric systems. The systems chosen for this study are (1) hydroxypropyl methylcellulose acetate succinate HF grade (HPMCAS-HF)-felodipine (FD) and (2) Soluplus (a graft copolymer of polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol)-FD. Samples containing different drug compositions were mixed, ball milled, and then analyzed by differential scanning calorimetry (DSC). The value of the drug-polymer interaction parameter χ was calculated from the crystalline drug melting depression data and extrapolated to lower temperatures. The interaction parameter χ was also calculated at 25 °C for both systems using the van Krevelen solubility parameter method. The rank order of interaction parameters of the two systems obtained at this temperature was comparable. Diagrams of drug-polymer temperature-composition and free energy of mixing (ΔG(mix)) were constructed for both systems. The maximum crystalline drug solubility and amorphous drug miscibility may be predicted based on the phase diagrams. Hyper-DSC was used to assess the validity of constructed phase diagrams by annealing solid dispersions at specific drug loadings. Three different samples for each polymer were selected to represent different regions within the phase diagram.

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.

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide

NASA Astrophysics Data System (ADS)

Mao, Dongsen; Lu, Guanzhong

2007-02-01

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO 2-ZrO 2 mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO 2-ZrO 2 into a crystalline ZrTiO 4 compound, while a larger amount of boria (⩾8 wt%) promotes the crystallization process. FT-IR spectroscopy and 11B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO 4 units delay, while a build-up of trigonal BO 3 promote, the crystallization of amorphous TiO 2-ZrO 2 to form ZrTiO 4 crystals.

Ambient-temperature NO oxidation over amorphous CrOx-ZrO 2 mixed oxide catalysts: Significant promoting effect of ZrO 2

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

Wang, Aiyong; Guo, Yanglong; Gao, Feng

2017-03-01

Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures are synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. Over best performing catalysts, 100% NO conversion can be maintained up to 30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure is found to be critical for these catalysts to maintain high activity and durability. Cr/M (M=Co, Femore » and Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature are important criteria for the synthesis of the highly active catalysts. This work was supported by National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang gratefully acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. Department of Energy (DOE) by Battelle. FG and CHFP are supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.« 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

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.

Elucidation and visualization of solid-state transformation and mixing in a pharmaceutical mini hot melt extrusion process using in-line Raman spectroscopy.

PubMed

Van Renterghem, Jeroen; Kumar, Ashish; Vervaet, Chris; Remon, Jean Paul; Nopens, Ingmar; Vander Heyden, Yvan; De Beer, Thomas

2017-01-30

Mixing of raw materials (drug+polymer) in the investigated mini pharma melt extruder is achieved by using co-rotating conical twin screws and an internal recirculation channel. In-line Raman spectroscopy was implemented in the barrels, allowing monitoring of the melt during processing. The aim of this study was twofold: to investigate (I) the influence of key process parameters (screw speed - barrel temperature) upon the product solid-state transformation during processing of a sustained release formulation in recirculation mode; (II) the influence of process parameters (screw speed - barrel temperature - recirculation time) upon mixing of a crystalline drug (tracer) in an amorphous polymer carrier by means of residence time distribution (RTD) measurements. The results indicated a faster mixing endpoint with increasing screw speed. Processing a high drug load formulation above the drug melting temperature resulted in the production of amorphous drug whereas processing below the drug melting point produced solid dispersions with partially amorphous/crystalline drug. Furthermore, increasing the screw speed resulted in lower drug crystallinity of the solid dispersion. RTD measurements elucidated the improved mixing capacity when using the recirculation channel. In-line Raman spectroscopy has shown to be an adequate PAT-tool for product solid-state monitoring and elucidation of the mixing behavior during processing in a mini extruder. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Broadband wavelength conversion in hydrogenated amorphous silicon waveguide with silicon nitride layer

NASA Astrophysics Data System (ADS)

Wang, Jiang; Li, Yongfang; Wang, Zhaolu; Han, Jing; Huang, Nan; Liu, Hongjun

2018-01-01

Broadband wavelength conversion based on degenerate four-wave mixing is theoretically investigated in a hydrogenated amorphous silicon (a-Si:H) waveguide with silicon nitride inter-cladding layer (a-Si:HN). We have found that enhancement of the non-linear effect of a-Si:H waveguide nitride intermediate layer facilitates broadband wavelength conversion. Conversion bandwidth of 490 nm and conversion efficiency of 11.4 dB were achieved in a numerical simulation of a 4 mm-long a-Si:HN waveguide under 1.55 μm continuous wave pumping. This broadband continuous-wave wavelength converter has potential applications in photonic networks, a type of readily manufactured low-cost highly integrated optical circuits.

Enhancement of the physical stability of amorphous indomethacin by mixing it with octaacetylmaltose. inter and intra molecular studies.

PubMed

Kaminska, E; Adrjanowicz, K; Zakowiecki, D; Milanowski, B; Tarnacka, M; Hawelek, L; Dulski, M; Pilch, J; Smolka, W; Kaczmarczyk-Sedlak, I; Kaminski, K

2014-10-01

To demonstrate a very effective and easy way of stabilization of amorphous indomethacin (IMC) by preparing binary mixtures with octaacetylmaltose (acMAL). In order to understand the origin of increased stability of amorphous system inter- and intramolecular interactions between IMC and acMAL were studied. The amorphous IMC, acMAL and binary mixtures (IMC-acMAL) with different weight ratios were analyzed by using Dielectric Spectroscopy (DS), Differential Scanning Calorimetry (DSC), Raman Spectroscopy, X-ray Diffraction (XRD), Infrared Spectroscopy (FTIR) and Quantitative Structure-Activity Relationship (QSAR). Our studies have revealed that indomethacin mixed with acetylated saccharide forms homogeneous mixture. Interestingly, even a small amount of modified maltose prevents from recrystallization of amorphous indomethacin. FTIR measurements and QSAR calculations have shown that octaacetylmaltose significantly affects the concentration of indomethacin dimers. Moreover, with increasing the amount of acMAL in the amorphous solid dispersion molecular interactions between matrix and API become more dominant than IMC-IMC ones. Structural investigations with the use of X-ray diffraction technique have demonstrated that binary mixture of indomethacin with acMAL does not recrystallize upon storage at room temperature for more than 1.5 year. Finally, it was shown that acMAL can be used to improve solubility of IMC. Acetylated derivative of maltose might be very effective agent to improve physical stability of amorphous indomethacin as well as to enhance its solubility. Intermolecular interactions between modified carbohydrate and IMC are likely to be responsible for increased stability effect in the glassy state.

Study on preparation of ultrafine amorphous particles by chemical reduction

NASA Astrophysics Data System (ADS)

Song, Xu; Yusheng, Xu; Huali, Jiang; Qing, Xue

1993-04-01

Ultrafine amorphous FeNiB powder was prepared by potassium borohydride reduction by mixing the aqueous solutions in a bath of supersonic oscillator. Different mixing ratios of potassium borohydride to metal salt were applied. Analysis of the composition of the sample and the Fe 2+ and Ni 2+ remaining in the filtrate after preparation shows that a quantity of KBH 4 about 1.5 times the stoichiometrical quantity is enough. Mössbauer measurements were performed at room temperature and it was found that excess KBH 4 makes no distinct difference in the spectra of the samples.

Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations.

PubMed

Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei

2017-02-14

Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiC x O 6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young's modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young's modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.

Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations

NASA Astrophysics Data System (ADS)

Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei

2017-02-01

Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiCxO6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young’s modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young’s modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.

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.

Flexible Electronics Powered by Mixed Metal Oxide Thin Film Transistors

NASA Astrophysics Data System (ADS)

Marrs, Michael

A low temperature amorphous oxide thin film transistor (TFT) and amorphous silicon PIN diode backplane technology for large area flexible digital x-ray detectors has been developed to create 7.9-in. diagonal backplanes. The critical steps in the evolution of the backplane process include the qualification and optimization of the low temperature (200 °C) metal oxide TFT and a-Si PIN photodiode process, the stability of the devices under forward and reverse bias stress, the transfer of the process to flexible plastic substrates, and the fabrication and assembly of the flexible detectors. Mixed oxide semiconductor TFTs on flexible plastic substrates suffer from performance and stability issues related to the maximum processing temperature limitation of the polymer. A novel device architecture based upon a dual active layer improves both the performance and stability. Devices are directly fabricated below 200 ºC on a polyethylene naphthalate (PEN) substrate using mixed metal oxides of either zinc indium oxide (ZIO) or indium gallium zinc oxide (IGZO) as the active semiconductor. The dual active layer architecture allows for adjustment to the saturation mobility and threshold voltage stability without the requirement of high temperature annealing, which is not compatible with flexible plastic substrates like PEN. The device performance and stability is strongly dependent upon the composition of the mixed metal oxide; this dependency provides a simple route to improving the threshold voltage stability and drive performance. By switching from a single to a dual active layer, the saturation mobility increases from 1.2 cm2/V-s to 18.0 cm2/V-s, while the rate of the threshold voltage shift decreases by an order of magnitude. This approach could assist in enabling the production of devices on flexible substrates using amorphous oxide semiconductors. Low temperature (200°C) processed amorphous silicon photodiodes were developed successfully by balancing the tradeoffs between low temperature and low stress (less than -70 MPa compressive) and device performance. Devices with a dark current of less than 1.0 pA/mm2 and a quantum efficiency of 68% have been demonstrated. Alternative processing techniques, such as pixelating the PIN diode and using organic photodiodes have also been explored for applications where extreme flexibility is desired.

Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks

NASA Astrophysics Data System (ADS)

Fu, Guopeng; Dempsey, Janel; Izaki, Kosuke; Adachi, Kaoru; Tsukahara, Yasuhisa; Kyu, Thein

2017-08-01

In an effort to fabricate highly conductive, stable solid-state polymer electrolyte membranes (PEM), polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction between polyethylene glycol diamine and ethylene carbonate. Subsequently, dimethacrylate groups were chemically attached to both ends of PEGBC to afford polyethylene glycol-bis-carbamate dimethacrylate (PEGBCDMA) precursor having crosslinking capability. The melt-mixed ternary mixtures consisting of PEGBCDMA, succinonitrile plasticizer, and lithium trifluorosulphonyl imide salt were completely miscible in a wide compositional range. Upon photo-crosslinking, the neat PEGBCDMA network was completely amorphous exhibiting higher tensile strength, modulus, and extensibility relative to polyethylene glycol diacrylate (PEGDA) counterpart. Likewise, the succinonitrile-plasticized PEM network containing PEGBCDMA remained completely amorphous and transparent upon photo-crosslinking, showing superionic conductivity, improved thermal stability, and superior tensile properties with improved capacity retention during charge/discharge cycling as compared to the PEGDA-based PEM.

Atomistic and infrared study of CO-water amorphous ice onto olivine dust grain

NASA Astrophysics Data System (ADS)

Escamilla-Roa, Elizabeth; Moreno, Fernando; López-Moreno, J. Juan; Sainz-Díaz, C. Ignacio

2017-01-01

This work is a study of CO and H2O molecules as adsorbates that interact on the surface of olivine dust grains. Olivine (forsterite) is present on the Earth, planetary dust, in the interstellar medium (ISM) and in particular in comets. The composition of amorphous ice is very important for the interpretation of processes that occur in the solar system and the ISM. Dust particles in ISM are composed of a heterogeneous mixture of amorphous or crystalline silicates (e.g. olivine) organic material, carbon, and other minor constituents. These dust grains are embedded in a matrix of ices, such as H2O, CO, CO2, NH3, and CH4. We consider that any amorphous ice will interact and grow faster on dust grain surfaces. In this work we explore the adsorption of CO-H2O amorphous ice onto several (100) forsterite surfaces (dipolar and non-dipolar), by using first principle calculations based on density functional theory (DFT). These models are applied to two possible situations: i) adsorption of CO molecules mixed into an amorphous ice matrix (gas mixture) and adsorbed directly onto the forsterite surface. This interaction has lower adsorption energy than polar molecules (H2O and NH3) adsorbed on this surface; ii) adsorption of CO when the surface has previously been covered by amorphous water ice (onion model). In this case the calculations show that adsorption energy is low, indicating that this interaction is weak and therefore the CO can be desorbed with a small increase of temperature. Vibration spectroscopy for the most stable complex was also studied and the frequencies were in good agreement with experimental frequency values.

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.

Magnetic field effect on the optoelectronic response of amorphous hydrogenated silicon

NASA Astrophysics Data System (ADS)

McLaughlin, Ryan; Sun, Dali; Zhang, Chuang; Ehrenfreund, Eitan; Vardeny, Zeev Valy

We have studied the magneto-photoluminescence and magneto photoconductivity in amorphous hydrogenated silicon (a-Si:H) thin films and devices as a function of temperature up to field of 5 Tesla. The magnetic field effects (MFE) are interpreted as spin mixing between spin-singlet and spin-triplet charge pairs due to the ''delta- g'' mechanism that is based on the g-value difference between the paired electron and hole, which directly affects the rate of radiative recombination and charge carrier separation, respectively. We found that the MFE(B) response does not form a Lorentzian (that is expected from the ''delta- g'' mechanism) due to disorder in the film that results in a broad distribution of e-h recombination rates, which could be extracted directly by time-resolved photoluminescence.

Quantitative determination of amorphous cyclosporine in crystalline cyclosporine samples by Fourier transform infrared spectroscopy.

PubMed

Bertacche, Vittorio; Pini, Elena; Stradi, Riccardo; Stratta, Fabio

2006-01-01

The purpose of this study is the development of a quantification method to detect the amount of amorphous cyclosporine using Fourier transform infrared (FTIR) spectroscopy. The mixing of different percentages of crystalline cyclosporine with amorphous cyclosporine was used to obtain a set of standards, composed of cyclosporine samples characterized by different percentages of amorphous cyclosporine. Using a wavelength range of 450-4,000 cm(-1), FTIR spectra were obtained from samples in potassium bromide pellets and then a partial least squares (PLS) model was exploited to correlate the features of the FTIR spectra with the percentage of amorphous cyclosporine in the samples. This model gave a standard error of estimate (SEE) of 0.3562, with an r value of 0.9971 and a standard error of prediction (SEP) of 0.4168, which derives from the cross validation function used to check the precision of the model. Statistical values reveal the applicability of the method to the quantitative determination of amorphous cyclosporine in crystalline cyclosporine samples.

Combination of struvite pyrolysate recycling with mixed-base technology for removing ammonium from fertilizer wastewater.

PubMed

Yu, Rongtai; Geng, Jinju; Ren, Hongqiang; Wang, Yanru; Xu, Ke

2012-11-01

Removal of ammonium from wastewater via struvite (MAP) pyrolysate recycling combined with a mixed-base NaOH/Mg(OH)(2) technology was investigated, and the phosphate and magnesium concentration in the supernatant were measured. The optimal parameters for acidolysis were a pH of 1; temperature of 120°C and time of 2h. The presence of derivatives of amorphous magnesium hydrogen phosphate (MgHPO(4)), namely magnesium phosphate (Mg(3)(PO(4))(2)) and magnesium pyrophosphate (Mg(2)P(2)O(7)) were verified by experiment. The ammonium removal ratio in this combined mixed-base technology was 96.8% in the first cycle, 80.6% in the second, and 81.0% after acidolysis. The phosphate and magnesium ions concentration in the supernatant were about 1mg/L and 40 mg/L, respectively. The grain size of MAP was 1.52 nm without seeding and 1.79 nm with seeding, and the growth rate of MAP was 17.6%. Copyright © 2012 Elsevier Ltd. All rights reserved.

A Molecular-Level View of the Physical Stability of Amorphous Solid Dispersions

NASA Astrophysics Data System (ADS)

Yuan, Xiaoda

Many pharmaceutical compounds being developed in recent years are poorly soluble in water. This has led to insufficient oral bioavailability of many compounds in vitro. The amorphous formulation is one of the promising techniques to increase the oral bioavailability of these poorly water-soluble compounds. However, an amorphous drug substance is inherently unstable because it is a high energy form. In order to increase the physical stability, the amorphous drug is often formulated with a suitable polymer to form an amorphous solid dispersion. Previous research has suggested that the formation of an intimately mixed drug-polymer mixture contributes to the stabilization of the amorphous drug compound. The goal of this research is to better understand the role of miscibility, molecular interactions and mobility on the physical stability of amorphous solid dispersions. Methods were developed to detect different degrees of miscibility on nanometer scale and to quantify the extent of hydrogen-bonding interactions between the drug and the polymer. Miscibility, hydrogen-bonding interactions and molecular mobility were correlated with physical stability during a six-month period using three model systems. Overall, this research provides molecular-level insights into many factors that govern the physical stability of amorphous solid dispersions which can lead to a more effective design of stable amorphous formulations.

Anisotropic etching of amorphous perfluoropolymer films in oxygen-based inductively coupled plasmas

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

Ono, Takao; Akagi, Takanori; Center for NanoBio Integration, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656

2009-01-01

An amorphous perfluoropolymer, 'Cytop' (Asahi Glass Co., Ltd.), is a preferable material for the fabrication of micro total analysis system devices because of its superior optical transparency over a wide wavelength range and low refractive index of 1.34, which is almost the same as that of water, as well as excellent chemical stability. To establish the precise microfabrication technology for this unique resin, the dry etching of the amorphous perfluoropolymer in Ar/O{sub 2} low-pressure inductively coupled plasma has been studied. A relatively high etch rate of approximately 6.3 {mu}m/min at maximum and highly anisotropic etched features was attained. Plasma measurementsmore » by a single Langmuir probe technique and actinometry revealed that etching is dominated by ion-assisted surface desorption above a 10%O{sub 2} mixing ratio, whereas the supply of active oxygen species is the rate-limiting process below 10%. Moreover, angled x-ray photoelectron spectroscopy measurements of an etched trench pattern revealed that a high anisotropy is attributed to the formation of a carbon-rich sidewall protection layer.« less

Proposed truncated Cu-Hf tight-binding potential to study the crystal-to-amorphous phase transition

NASA Astrophysics Data System (ADS)

Cui, Yuanyuan; Li, Jiahao; Dai, Ye; Liu, Baixin

2010-09-01

Proposed truncated Cu-Hf tight-binding potential was constructed by fitting the physical properties of Cu, Hf, and their stable compounds, i.e., Cu5Hf, Cu8Hf3, Cu10Hf7, and CuHf2. Based on the constructed potentials, molecular dynamics simulations were carried out to compare the relative stability of the crystalline solid solution and the disordered state. Simulation results not only reveal that the physical origin of crystal-to-amorphous transition is the crystalline lattice collapsing when the solute atoms exceeding the critical concentration, but also predict that the glass forming range (GFR) of the Cu-Hf system is 21-77 at. % Cu, which covers the GFRs determined by various metallic glass-producing techniques. Ion beam mixing experiments of the Cu-Hf system were conducted using 200 keV xenon ions and the results show that a uniform amorphous phase can be obtained in the Cu23Hf77 sample, matching well with the GFR determined by the interatomic potential, which, in turn, provides additional evidence to the relevance of the constructed Cu-Hf potential.

Iron-based amorphous alloys and methods of synthesizing iron-based amorphous alloys

DOEpatents

Saw, Cheng Kiong; Bauer, William A.; Choi, Jor-Shan; Day, Dan; Farmer, Joseph C.

2016-05-03

A method according to one embodiment includes combining an amorphous iron-based alloy and at least one metal selected from a group consisting of molybdenum, chromium, tungsten, boron, gadolinium, nickel phosphorous, yttrium, and alloys thereof to form a mixture, wherein the at least one metal is present in the mixture from about 5 atomic percent (at %) to about 55 at %; and ball milling the mixture at least until an amorphous alloy of the iron-based alloy and the at least one metal is formed. Several amorphous iron-based metal alloys are also presented, including corrosion-resistant amorphous iron-based metal alloys and radiation-shielding amorphous iron-based metal alloys.

Dose dependence of radiation damage in nano-structured amorphous SiOC/crystalline Fe composite

DOE PAGES

Su, Qing; Price, Lloyd; Shao, Lin; ...

2015-10-29

Here, through examination of radiation tolerance properties of amorphous silicon oxycarbide (SiOC) and crystalline Fe composite to averaged damage levels, from approximately 8 to 30 displacements per atom (dpa), we demonstrated that the Fe/SiOC interface and the Fe/amorphous Fe xSi yO z interface act as efficient defect sinks and promote the recombination of vacancies and interstitials. For thick Fe/SiOC multilayers, a clear Fe/SiOC interface remained and no irradiation-induced mixing was observed even after 32 dpa. For thin Fe/SiOC multilayers, an amorphous Fe xSi yO z intermixed layer was observed to form at 8 dpa, but no further layer growth wasmore » observed for higher dpa levels.« less

Poly(methyl methacrylate) coating of soft magnetic amorphous and crystalline Fe,Co-B nanoparticles by chemical reduction.

PubMed

Fernández Barquín, L; Yedra Martínez, A; Rodríguez Fernández, L; Rojas, D P; Murphy, F J; Alba Venero, D; Ruiz González, L; González-Calbet, J; Fdez-Gubieda, M L; Pankhurst, Q A

2012-03-01

The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, Mössbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.

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.

Low-viscosity hydroxypropylcellulose (HPC) grades SL and SSL: versatile pharmaceutical polymers for dissolution enhancement, controlled release, and pharmaceutical processing.

PubMed

Sarode, Ashish; Wang, Peng; Cote, Catherine; Worthen, David R

2013-03-01

Hydroxypropylcellulose (HPC)-SL and -SSL, low-viscosity hydroxypropylcellulose polymers, are versatile pharmaceutical excipients. The utility of HPC polymers was assessed for both dissolution enhancement and sustained release of pharmaceutical drugs using various processing techniques. The BCS class II drugs carbamazepine (CBZ), hydrochlorthiazide, and phenytoin (PHT) were hot melt mixed (HMM) with various polymers. PHT formulations produced by solvent evaporation (SE) and ball milling (BM) were prepared using HPC-SSL. HMM formulations of BCS class I chlorpheniramine maleate (CPM) were prepared using HPC-SL and -SSL. These solid dispersions (SDs) manufactured using different processes were evaluated for amorphous transformation and dissolution characteristics. Drug degradation because of HMM processing was also assessed. Amorphous conversion using HMM could be achieved only for relatively low-melting CBZ and CPM. SE and BM did not produce amorphous SDs of PHT using HPC-SSL. Chemical stability of all the drugs was maintained using HPC during the HMM process. Dissolution enhancement was observed in HPC-based HMMs and compared well to other polymers. The dissolution enhancement of PHT was in the order of SE>BM>HMM>physical mixtures, as compared to the pure drug, perhaps due to more intimate mixing that occurred during SE and BM than in HMM. Dissolution of CPM could be significantly sustained in simulated gastric and intestinal fluids using HPC polymers. These studies revealed that low-viscosity HPC-SL and -SSL can be employed to produce chemically stable SDs of poorly as well as highly water-soluble drugs using various pharmaceutical processes in order to control drug dissolution.

High-Nitrogen-Based Pyrotechnics: Longer- and Brighter-Burning, Perchlorate-Free, Red-Light Illuminants for Military and Civilian Applications

DTIC Science & Technology

2011-01-01

combustion of these materials. To address the aforementioned perchlorate issues, an effort was initiated by ARDEC to remove potassium per- chlorate ...with acceptable burn times for pyrotechnic applications by using potassium nitrate– amorphous boron–crystalline boron/boron carbide–epoxy binder mixtures...3,4] Moreover, it was discovered by ARDEC that a potassium nitrate–boron carbide–epoxy binder mix- ture alone was able to generate suitable green

Solvothermal growth of a ruthenium metal-organic framework featuring HKUST-1 structure type as thin films on oxide surfaces.

PubMed

Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat; Wang, Yuemin; Walleck, Stephan; Glaser, Thorsten; Fischer, Roland A

2011-08-14

Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1). This journal is © The Royal Society of Chemistry 2011

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.

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

On the Mass Fractal Character of Si-Based Structural Networks in Amorphous Polymer Derived Ceramics

PubMed Central

Sen, Sabyasachi; Widgeon, Scarlett

2015-01-01

The intermediate-range packing of SiNxC4−x (0 ≤ x ≤ 4) tetrahedra in polysilycarbodiimide and polysilazane-derived amorphous SiCN ceramics is investigated using 29Si spin-lattice relaxation nuclear magnetic resonance (SLR NMR) spectroscopy. The SiCN network in the polysilylcarbodiimide-derived ceramic consists predominantly of SiN4 tetrahedra that are characterized by a 3-dimensional spatial distribution signifying compact packing of such units to form amorphous Si3N4 clusters. On the other hand, the SiCN network of the polysilazane-derived ceramic is characterized by mixed bonded SiNxC4−x tetrahedra that are inefficiently packed with a mass fractal dimension of Df ~2.5 that is significantly lower than the embedding Euclidean dimension (D = 3). This result unequivocally confirms the hypothesis that the presence of dissimilar atoms, namely, 4-coordinated C and 3-coordinated N, in the nearest neighbor environment of Si along with some exclusion in connectivity between SiCxN4−x tetrahedra with widely different N:C ratios and the absence of bonding between C and N result in steric hindrance to an efficient packing of these structural units. It is noted that similar inefficiencies in packing are observed in polymer-derived amorphous SiOC ceramics as well as in proteins and binary hard sphere systems. PMID:28347016

Atomistic modeling of crystal-to-amorphous transition and associated kinetics in the Ni-Nb system by molecular dynamics simulations.

PubMed

Dai, X D; Li, J H; Liu, B X

2005-03-17

With the aid of ab initio calculations, an n-body potential of the Ni-Nb system is constructed under the Finnis-Sinclair formalism and the constructed potential is capable of not only reproducing some static physical properties but also revealing the atomistic mechanism of crystal-to-amorphous transition and associated kinetics. With application of the constructed potential, molecular dynamics simulations using the solid solution models reveal that the physical origin of crystal-to-amorphous transition is the crystalline lattice collapsing while the solute atoms are exceeding the critical solid solubilities, which are determined to be 19 atom % Ni and 13 atom % Nb for the Nb- and Ni-based solid solutions, respectively. It follows that an intrinsic glass-forming ability of the Ni-Nb system is within 19-87 atom % Ni, which matches well with that observed in ion beam mixing/solid-state reaction experiments. Simulations using the Nb/Ni/Nb (Ni/Nb/Ni) sandwich models indicate that the amorphous layer at the interfaces grows in a layer-by-layer mode and that, upon dissolving solute atoms, the Ni lattice approaches and exceeds its critical solid solubility faster than the Nb lattice, revealing an asymmetric behavior in growth kinetics. Moreover, an energy diagram is obtained by computing the energetic sequence of the Ni(x)Nb(100)(-)(x) alloy in fcc, bcc, and amorphous structures, respectively, over the entire composition range, and the diagram could serve as a guide for predicting the metastable alloy formation in the Ni-Nb system.

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.

Large Scale Synthesis and Light Emitting Fibers of Tailor-Made Graphene Quantum Dots

PubMed Central

Park, Hun; Hyun Noh, Sung; Hye Lee, Ji; Jun Lee, Won; Yun Jaung, Jae; Geol Lee, Seung; Hee Han, Tae

2015-01-01

Graphene oxide (GO), which is an oxidized form of graphene, has a mixed structure consisting of graphitic crystallites of sp2 hybridized carbon and amorphous regions. In this work, we present a straightforward route for preparing graphene-based quantum dots (GQDs) by extraction of the crystallites from the amorphous matrix of the GO sheets. GQDs with controlled functionality are readily prepared by varying the reaction temperature, which results in precise tunability of their optical properties. Here, it was concluded that the tunable optical properties of GQDs are a result of the different fraction of chemical functionalities present. The synthesis approach presented in this paper provides an efficient strategy for achieving large-scale production and long-time optical stability of the GQDs, and the hybrid assembly of GQD and polymer has potential applications as photoluminescent fibers or films. PMID:26383257

Molecular Dynamics, Recrystallization Behavior, and Water Solubility of the Amorphous Anticancer Agent Bicalutamide and Its Polyvinylpyrrolidone Mixtures.

PubMed

Szczurek, Justyna; Rams-Baron, Marzena; Knapik-Kowalczuk, Justyna; Antosik, Agata; Szafraniec, Joanna; Jamróz, Witold; Dulski, Mateusz; Jachowicz, Renata; Paluch, Marian

2017-04-03

In this paper, we investigated the molecular mobility and physical stability of amorphous bicalutamide, a poorly water-soluble drug widely used in prostate cancer treatment. Our broadband dielectric spectroscopy measurements and differential scanning calorimetry studies revealed that amorphous BIC is a moderately fragile material with a strong tendency to recrystallize from the amorphous state. However, mixing the drug with polymer polyvinylpyrrolidone results in a substantial improvement of physical stability attributed to the antiplasticizing effect governed by the polymer additive. Furthermore, IR study demonstrated the existence of specific interactions between the drug and excipient. We found out that preparation of bicalutamide-polyvinylpyrrolidone mixture in a 2-1 weight ratio completely hinder material recrystallization. Moreover, we determined the time-scale of structural relaxation in the glassy state for investigated materials. Because molecular mobility is considered an important factor governing crystallization behavior, such information was used to approximate the long-term physical stability of an amorphous drug and drug-polymer systems upon their storage at room temperature. Moreover, we found that such systems have distinctly higher water solubility and dissolution rate in comparison to the pure amorphous form, indicating the genuine formulation potential of the proposed approach.

Amorphous and crystalline TiO2 nanotube arrays for enhanced Li-ion intercalation properties.

PubMed

Guan, Dongsheng; Cai, Chuan; Wang, Ying

2011-04-01

We have employed a simple process of anodizing Ti foils to prepare TiO2 nanotube arrays which show enhanced electrochemical properties for applications as Li-ion battery electrode materials. The lengths and pore diameters of TiO2 nanotubes can be finely tuned by varying voltage, electrolyte composition, or anodization time. The as-prepared nanotubes are amorphous and can be converted into anatase nanotubes with heat treatment at 480 degrees C. Rutile crystallites emerge in the anatase nanotube when the annealing temperature is increased to 580 degrees C, resulting in TiO2 nanotubes of mixed phases. The morphological features of nanotubes remain unchanged after annealing. Li-ion insertion performance has been studied for amorphous and crystalline TiO2 nanotube arrays. Amorphous nanotubes with a length of 3.0 microm and an outer diameter of 125 nm deliver a capacity of 91.2 microA h cm(-2) at a current density of 400 microA cm(-2), while those with a length of 25 microm and an outer diameter of 158 nm display a capacity of 533 microA h cm-2. When the 3-microm long nanotubes become crystalline, they deliver lower capacities: the anatase nanotubes and nanotubes of mixed phases show capacities of 53.8 microA h cm-2 and 63.1 microA h cm(-2), respectively at the same current density. The amorphous nanotubes show excellent capacity retention ability over 50 cycles. The cycled nanotubes show little change in morphology compared to the nanotubes before electrochemical cycling. All the TiO2 nanotubes demonstrate higher capacities than amorphous TiO2 compact layer reported in literature. The amorphous TiO2 nanotubes with a length of 1.9 microm exhibit a capacity five times higher than that of TiO2 compact layer even when the nanotube array is cycled at a current density 80 times higher than that for the compact layer. These results suggest that anodic TiO2 nanotube arrays are promising electrode materials for rechargeable Li-ion batteries.

Availability of ferric iron for microbial reduction in bottom sediments of the freshwater tidal Potomac River

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

Lovley, D.R.; Phillips, E.J.P.

1986-10-01

The distribution of Fe(III), its availability for microbial reduction, and factors controlling Fe(III) availability were investigated in sediments from a freshwater site in the Potomac River Estuary. Fe(III) reduction in sediments incubated under anaerobic conditions and depth profiles of oxalate-extractable Fe(III) indicated that Fe(III) reduction was limited to depths of 4 cm or less, with the most intense Fe(III) reduction in the top 1 cm. In incubations of the upper 4 cm of the sediments, Fe(III) reduction was as important as methane production as a pathway for anaerobic electron flow because of the high rates of Fe(III) reduction in themore » 0- 0.5-cm interval. Most of the oxalate-extractable Fe(III) in the sediments was not reduced and persisted to a depth of at least 20 cm. The incomplete reduction was not the result of a lack of suitable electron donors. The oxalate-extractable Fe(III) that was preserved in the sediments was considered to be in a form other than amorphous Fe(III) oxyhydroxide, since synthetic amorphous Fe(III) oxyhydroxide, amorphous Fe(III) oxyhydroxide adsorbed onto clay, and amorphous Fe(III) oxyhydroxide saturated with adsorbed phosphate or fulvic acids were all readily reduced. Fe/sub 3/O/sub 4/ and the mixed Fe(III)-Fe(II) compound(s) that were produced during the reduction of amorphous Fe(III) oxyhydroxide in an enrichment culture were oxalate extractable but were not reduced, suggesting that mixed Fe(III)-Fe(II) compounds might account for the persistence of oxalate-extractable Fe(III) in the sediments.« less

Xenon-ion-induced and thermal mixing of Co/Si bilayers and their interplay

NASA Astrophysics Data System (ADS)

Novaković, M.; Zhang, K.; Popović, M.; Bibić, N.; Hofsäss, H.; Lieb, K. P.

2011-05-01

Studies on ion-irradiated transition-metal/silicon bilayers demonstrate that interface mixing and silicide phase formation depend sensitively on the ion and film parameters, including the structure of the metal/Si interface. Thin Co layers e-gun evaporated to a thickness of 50 nm on Si(1 0 0) wafers were bombarded at room temperature with 400-keV Xe + ions at fluences of up to 3 × 10 16 cm -2. We used either crystalline or pre-amorphized Si wafers the latter ones prepared by 1.0-keV Ar-ion implantation. The as-deposited or Xe-ion-irradiated samples were then isochronally annealed at temperatures up to 700 °C. Changes of the bilayer structures induced by ion irradiation and/or annealing were investigated with RBS, XRD and HRTEM. The mixing rate for the Co/c-Si couples, Δ σ2/ Φ = 3.0(4) nm 4, is higher than the value expected for ballistic mixing and about half the value typical for spike mixing. Mixing of pre-amorphized Si is much weaker relative to crystalline Si wafers, contrary to previous results obtained for Fe/Si bilayers. Annealing of irradiated samples produces very similar interdiffusion and phase formation patterns above 400 °C as in the non-irradiated Co/Si bilayers: the phase evolution follows the sequence Co 2Si → CoSi → CoSi 2.

Synthesis and characterisation of composite based biohydroxyapatite bovine bone mandible waste (BHAp) doped with 10 wt % amorphous SiO{sub 2} from rice husk by solid state reaction

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

Asmi, Dwi, E-mail: dwiasmi82@yahoo.com, E-mail: dwi.asmi@fmipa.unila.ac.id; Sulaiman, Ahmad, E-mail: ahmadsulaiman@yahoo.co.id; Oktavia, Irene Lucky, E-mail: ireneluckyo@gmail.com

Effect of 10 wt% amorphous SiO{sub 2} from rice husk addition on the microstructures of biohydroxyapatite (BHAp) obtained from bovine bone was synthesized by solid state reaction. In this study, biohydroxyapatite powder was obtained from bovine bone mandible waste heat treated at 800 °C for 5 h and amorphous SiO{sub 2} powder was extracted from citric acid leaching of rice husk followed by combustion at 700°C for 5 h. The composite powder then mixed and sintered at 1200 °C for 3 h. X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and Scanning electron microscopy (SEM) techniques are utilized to characterize the phase relations,more » functional group present and morphology of the sample. The study has revealed that the processing procedures played an important role in microstructural development of BHAp-10 wt% SiO{sub 2} composite. The XRD study of the raw material revealed that the primary phase material in the heat treated of bovine bone mandible waste is hydroxyapatite and in the combustion of rice husk is amorphous SiO{sub 2}. However, in the composite the hydroxyapatite, β-tricalcium phosphate, and calcium phosphate silicate were observed. The FTIR result show that the hydroxyl stretching band in the composite decrease compared with those of hydroxyapatite spectra and the evolution of morphology was occurred in the composite.« less

Facile sonochemical synthesis of amorphous NiFe-(oxy)hydroxide nanoparticles as superior electrocatalysts for oxygen evolution reaction.

PubMed

Lee, Eunjik; Park, Ah-Hyeon; Park, Hyun-Uk; Kwon, Young-Uk

2018-01-01

In this work, we present facile synthesis of amorphous Ni/Fe mixed (oxy)hydroxide (NiFe(H)) nanoparticles (NPs) and their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline media. a-NiFe(H) NPs have received lots of attention as OER electrocatalysts with many desirable properties. By using a simple sonochemical route, we prepared amorphous Ni and Fe-alkoxide (NiFe(A)) NPs whose composition can be controlled in the entire composition range (Ni 100-x Fe x , 0≤x≤1). These samples are composed of extremely small NiFe(A) NPs with Ni and Fe atoms homogeneously distributed. NiFe(A) NPs are readily converted into corresponding electrocatalytically active NiFe(H) NP by a simple electrochemical treatment. Electrochemical analysis data show that the OER activity of amorphous NiFe(H) samples follows the volcano-type trend when plotted against the Fe content. Ni 70 Fe 30 (H) sample showed the lowest overpotential of 292mV at 10mAcm -2 geo and the lowest Tafel slope of 30.4mVdec -1 , outperforming IrO x /C (326mV, 41.7mVdec -1 ). Our samples are highly durable based on the chronopotentiometry data at the current density of 10mAcm -2 geo for 2h which show that Ni 70 Fe 30 sample maintains the steady-state potential, contrary to the time-varying IrO x /C. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and characterisation of composite based biohydroxyapatite bovine bone mandible waste (BHAp) doped with 10 wt % amorphous SiO2 from rice husk by solid state reaction

NASA Astrophysics Data System (ADS)

Asmi, Dwi; Sulaiman, Ahmad; Oktavia, Irene Lucky; Badaruddin, Muhammad; Zulfia, Anne

2016-04-01

Effect of 10 wt% amorphous SiO2 from rice husk addition on the microstructures of biohydroxyapatite (BHAp) obtained from bovine bone was synthesized by solid state reaction. In this study, biohydroxyapatite powder was obtained from bovine bone mandible waste heat treated at 800 °C for 5 h and amorphous SiO2 powder was extracted from citric acid leaching of rice husk followed by combustion at 700°C for 5 h. The composite powder then mixed and sintered at 1200 °C for 3 h. X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and Scanning electron microscopy (SEM) techniques are utilized to characterize the phase relations, functional group present and morphology of the sample. The study has revealed that the processing procedures played an important role in microstructural development of BHAp-10 wt% SiO2 composite. The XRD study of the raw material revealed that the primary phase material in the heat treated of bovine bone mandible waste is hydroxyapatite and in the combustion of rice husk is amorphous SiO2. However, in the composite the hydroxyapatite, β-tricalcium phosphate, and calcium phosphate silicate were observed. The FTIR result show that the hydroxyl stretching band in the composite decrease compared with those of hydroxyapatite spectra and the evolution of morphology was occurred in the composite.

A Fundamental Approach to Developing Aluminium based Bulk Amorphous Alloys based on Stable Liquid Metal Structures and Electronic Equilibrium - 154041

DTIC Science & Technology

2017-03-28

AFRL-AFOSR-JP-TR-2017-0027 A Fundamental Approach to Developing Aluminium-based Bulk Amorphous Alloys based on Stable Liquid -Metal Structures and...to 16 Dec 2016 4.  TITLE AND SUBTITLE A Fundamental Approach to Developing Aluminium-based Bulk Amorphous Alloys based on Stable Liquid -Metal...including Al, Cu, Ni, Zr, Mg, Pd, Ga , Ca. Many new Al-based amorphous alloys were found within the numerous alloy systems studied in this project, and

Photochromic amorphous molecular materials and their applications

NASA Astrophysics Data System (ADS)

Shirota, Yasuhiko; Utsumi, Hisayuki; Ujike, Toshiki; Yoshikawa, Satoru; Moriwaki, Kazuyuki; Nagahama, Daisuke; Nakano, Hideyuki

2003-01-01

Two novel classes of photochromic amorphous molecular materials based on azobenzene and dithienylethene were designed and synthesized. They were found to readily form amorphous glasses with well-defined glass-transition temperatures when the melt samples were cooled on standing in air and to exhibit photochromism in their amorphous films as well as in solution. Photochromic properties of these materials are discussed in relation to their molecular structures. Surface relief grating was formed on the amorphous films of azobenzene-based photochromic amorphous molecular materials by irradiation with two coherent Ar + laser beams. Dual image was formed at the same location of the films of dithienylethene-based photochromic amorphous molecular materials by irradiation with two linearly polarized light beams perpendicular to each other.

Glass Forming Ability in the Equilibrium Immiscible Ag-Ta System Studied by Molecular Dynamics Simulation and Ion Beam Mixing

NASA Astrophysics Data System (ADS)

Zhao, Man; Dai, Xiaodong; Shen, Yixiong; Liu, Baixin

2008-07-01

For the equilibrium immiscible Ag-Ta system characterized by a positive heat of formation of +23 kJ/mol, a proved realistic extended Finnis-Sinclair potential is applied to study the crystal-to-amorphous transition through molecular dynamics simulations and a glass-forming range (GFR) of the Ag-Ta system is determined to be from 10 to 80 at. % of Ta, within which a disordered state is energetically favored than its crystalline counterpart of solid solution. In experiment, the uniform amorphous phases are indeed obtained, by ion beam mixing of far-from-equilibrium, in the Ag38Ta62, Ag30Ta70 and Ag20Ta80 Ag-Ta multilayered films, which fall within the GFR and thus confirm the relevance of the calculated GFR of the system.

Amorphization and thermal stability of aluminum-based nanoparticles prepared from the rapid cooling of nanodroplets: effect of iron addition.

PubMed

Xiao, Shifang; Li, Xiaofan; Deng, Huiqiu; Deng, Lei; Hu, Wangyu

2015-03-07

Despite an intensive investigation on bimetallic nanoparticles, little attention has been paid to their amorphization in the past few decades. The study of amorphization on a nanoscale is of considerable significance for the preparation of amorphous nanoparticles and bulk metallic glass. Herein, we pursue the amorphization process of Al-based nanoparticles with classic molecular dynamics simulations and local structural analysis techniques. By a comparative study of the amorphization of pure Al and Fe-doped Al-based nanodroplets in the course of rapid cooling, we find that Fe addition plays a very important role in the vitrification of Al-based nanodroplets. Owing to the subsurface segregated Fe atoms with their nearest neighbors tending to form relatively stable icosahedral (ICO) clusters, the Fe-centred cluster network near the surface effectively suppresses the crystallization of droplets from surface nucleation and growth as the concentration of Fe attains a certain value. The glass formation ability of nanodroplets is suggested to be enhanced by the high intrinsic inner pressure as a result of small size and surface tension, combined with the dopant-inhibited surface nucleation. In addition, the effect of the size and the added concentration of nanoparticles on amorphization and the thermal stability of the amorphous nanoparticles are discussed. Our findings reveal the amorphization mechanism in Fe-doped Al-based nanoparticles and provide a theoretical guidance for the design of amorphous materials.

Solution-grown silicon nanowires for lithium-ion battery anodes.

PubMed

Chan, Candace K; Patel, Reken N; O'Connell, Michael J; Korgel, Brian A; Cui, Yi

2010-03-23

Composite electrodes composed of silicon nanowires synthesized using the supercritical fluid-liquid-solid (SFLS) method mixed with amorphous carbon or carbon nanotubes were evaluated as Li-ion battery anodes. Carbon coating of the silicon nanowires using the pyrolysis of sugar was found to be crucial for making good electronic contact to the material. Using multiwalled carbon nanotubes as the conducting additive was found to be more effective for obtaining good cycling behavior than using amorphous carbon. Reversible capacities of 1500 mAh/g were observed for 30 cycles.

UNIDENTIFIED INFRARED EMISSION BANDS: PAHs or MAONs?

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

Sun Kwok; Yong Zhang, E-mail: sunkwok@hku.hk

2013-07-01

We suggest that the carrier of the unidentified infrared emission (UIE) bands is an amorphous carbonaceous solid with mixed aromatic/aliphatic structures, rather than free-flying polycyclic aromatic hydrocarbon molecules. Through spectral fittings of the astronomical spectra of the UIE bands, we show that a significant amount of the energy is emitted by the aliphatic component, implying that aliphatic groups are an essential part of the chemical structure. Arguments in favor of an amorphous, solid-state structure rather than a gas-phase molecule as a carrier of the UIE are also presented.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor.

PubMed

von Rohr, Fabian; Winiarski, Michał J; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-11-15

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.

Charged Nanowire-Directed Growth of Amorphous Calcium Carbonate Nanosheets in a Mixed Solvent for Biomimetic Composite Films.

PubMed

Liu, Yang-Yi; Liu, Lei; Chen, Si-Ming; Chang, Fu-Jia; Mao, Li-Bo; Gao, Huai-Ling; Ma, Tao; Yu, Shu-Hong

2018-05-22

Bio-inspired mineralization is an effective way for fabricating complex inorganic materials, which inspires us to develop new methods to synthesize materials with fascinating properties. In this article, we report that the charged tellurium nanowires (TeNWs) can be used as biomacromolecule analogues to direct the formation of amorphous calcium carbonate (ACC) nanosheets (ACCNs) in a mixed solvent. The effects of surface charges and the concentration of the TeNWs on the formation of ACCNs have been investigated. Particularly, the produced ACCNs can be functionalized by Fe 3 O 4 nanoparticles to produce magnetic ACC/Fe 3 O 4 hybrid nanosheets that can be used to construct ACC/Fe 3 O 4 composite films through a self-evaporation process. Moreover, sodium alginate-ACC nanocomposite films with remarkable toughness and good transmittance can also be fabricated by using such ACCNs as nanoscale building blocks. This mineralization approach in a mixed solvent using charged TeNWs as biomacromolecule analogues provides a new way for the synthesis of ACCNs, which can be used as nanoscale building blocks for the fabrication of biomimetic composite films.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K

NASA Technical Reports Server (NTRS)

Moore, M.; Ferrante, R.; Hudson, R.; Tanabe, T.; Nuth, J.

1993-01-01

Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.

Effect of characteristics of compounds on maintenance of an amorphous state in solid dispersion with crospovidone.

PubMed

Shibata, Yusuke; Fujii, Makiko; Kokudai, Makiko; Noda, Shinobu; Okada, Hideko; Kondoh, Masuo; Watanabe, Yoshiteru

2007-06-01

Solid dispersion (SD) of indomethacin with crospovidone (CrosPVP) shows useful characteristics for preparation of dosage forms. This study aimed to determine the types of drugs that could adopt a stable amorphous form in SD. Twenty compounds with various melting points (70-218 degrees C), molecular weights (135-504) and functional groups (amide, amino, carbonyl, hydroxyl, ketone etc.) were prepared in SD with CrosPVP. The CrosPVP SDs were prepared using a mechanical mixing and heating method. Melting point and molecular weight were found to have no influence on the ability of a compound to maintain an amorphous state in SD. All compounds containing hydrogen-bond-donor functional groups existed in an amorphous state in SD for at least 6 months. Infrared spectra suggested an interaction between the functional groups of these compounds and amide carbonyl group of CrosPVP. Compounds without hydrogen-bond-donor groups could not maintain an amorphous state and underwent recrystallization within 1 month. It was suggested that the presence of a hydrogen-bond-donor functional group in a compound is an important factor affecting the stable formation of SD with CrosPVP, which contains a hydrogen-bond acceptor.

First X-ray View of Martian Soil

NASA Image and Video Library

2012-10-30

This graphic shows results of the first analysis of Martian soil by the CheMin experiment on NASA Curiosity rover. The image reveals the presence of crystalline feldspar, pyroxenes and olivine mixed with some amorphous non-crystalline material.

Monte Carlo simulation of magnetic properties of mixed spin (3/2, 1) ferromagnetic and ferrimagnetic disordered binary alloys with amorphous structure

NASA Astrophysics Data System (ADS)

Motlagh, H. Nakhaei; Rezaei, G.

2018-01-01

Monte Carlo simulation is used to study the magnetic properties of mixed spin (3/2, 1) disordered binary alloys on simple cubic, hexagonal and amorphous magnetic ultra-thin films with 18 × 18 × 2 atoms. To this end, at the first approximation, the exchange coupling interaction between the spins is considered as a constant value and at the second one, the Ruderman-Kittel-Kasuya-Yosida (RKKY) model is used. Effects of concentration, structure, exchange interaction, single ion-anisotropy and the film size on the magnetic properties of disordered ferromagnetic and ferrimagnetic binary alloys are investigated. Our results indicate that the spontaneous magnetization and critical temperatures of rare earth-3d transition binary alloys are affected by these parameters. It is also found that in the ferrimagnetic state, the compensation temperature (Tcom) and the magnetic rearrangement temperature (TR) appear for some concentrations.

Visible light response, electrical transport, and amorphization in compressed organolead iodine perovskites.

PubMed

Ou, Tianji; Yan, Jiejuan; Xiao, Chuanhai; Shen, Wenshu; Liu, Cailong; Liu, Xizhe; Han, Yonghao; Ma, Yanzhang; Gao, Chunxiao

2016-06-02

Recent scientific advances on organic-inorganic hybrid perovskites are mainly focused on the improvement of power conversion efficiency. So far, how compression tunes their electronic and structural properties remains less understood. By combining in situ photocurrent, impedance spectroscopy, and X-ray diffraction (XRD) measurements, we have studied the electrical transport and structural properties of compressed CH3NH3PbI3 (MAPbI3) nanorods. The visible light response of MAPbI3 remains robust below 3 GPa while it is suppressed when it becomes amorphous. Pressure-induced electrical transport properties of MAPbI3 including resistance, relaxation frequency, and relative permittivity have been investigated under pressure up to 8.5 GPa by in situ impedance spectroscopy measurements. These results indicate that the discontinuous changes of these physical parameters occur around the structural phase transition pressure. The XRD studies of MAPbI3 under high pressure up to 20.9 GPa show that a phase transformation below 0.7 GPa, could be attributed to the tilting and distortion of PbI6 octahedra. And pressure-induced amorphization is reversible at a low density amorphous state but irreversible at a relatively higher density state. Furthermore, the MAPbI3 nanorods crush into nanopieces around 0.9 GPa which helps us to explain why the mixed phase of tetragonal and orthorhombic was observed at 0.5 GPa. The pressure modulated changes of electrical transport and visible light response properties open up a new approach for exploring CH3NH3PbI3-based photo-electronic applications.

Electromagnetic mixed waste processing system for asbestos decontamination

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

Kasevich, R.S.; Vaux, W.; Ulerich, N.

The overall objective of this three-phase program is to develop an integrated process for treating asbestos-containing material that is contaminated with radioactive and hazardous constituents. The integrated process will attempt to minimize processing and disposal costs. The objectives of Phase 1 were to establish the technical feasibility of asbestos decomposition, inorganic radionuclide nd heavy metal removal, and organic volatilization. Phase 1 resulted in the successful bench-scale demonstration of the elements required to develop a mixed waste treatment process for asbestos-containing material (ACM) contaminated with radioactive metals, heavy metals, and organics. Using the Phase 1 data, a conceptual process was developed.more » The Phase 2 program, currently in progress, is developing an integrated system design for ACM waste processing. The Phase 3 program will target demonstration of the mixed waste processing system at a DOE facility. The electromagnetic mixed waste processing system employs patented technologies to convert DOE asbestos to a non-hazardous, radionuclide-free, stable waste. The dry, contaminated asbestos is initially heated with radiofrequency energy to remove organic volatiles. Second,the radionuclides are removed by solvent extraction coupled with ion exchange solution treatment. Third, the ABCOV method converts the asbestos to an amorphous silica suspension at low temperature (100{degrees}C). Finally the amorphous silica is solidified for disposal.« less

Pre-treatment of multi-walled carbon nanotubes for polyetherimide mixed matrix hollow fiber membranes.

PubMed

Goh, P S; Ng, B C; Ismail, A F; Aziz, M; Hayashi, Y

2012-11-15

Mixed matrix hollow fibers composed of multi-walled carbon nanotubes (MWCNTs) and polyetherimide (PEI) were fabricated. Pre-treatment of MWCNTs was carried out prior to the incorporation into the polymer matrix using a simple and feasible two stages approach that involved dry air oxidation and surfactant dispersion. The characterizations of the surface treated MWCNTs using TEM and Raman spectroscopy have evidenced the effectiveness of dry air oxidation in eliminating undesired amorphous carbon and metal catalyst while surfactant dispersion using Triton X100 has suppressed the agglomeration of MWCNTs. The resultant mixed matrix hollow fibers were applied for O(2)/N(2) pure gas separation. Interestingly, it was found that removal of disordered amorphous carbons and metal particles has allowed the hollow structures to be more accessible for the fast and smooth transport of gas molecules, hence resulted in noticeable improvement in the gas separation properties. The composite hollow fibers embedded with the surface modified MWCNTs showed increase in permeability as much as 60% while maintaining the selectivity of the O(2)/N(2) gas pair. This study highlights the necessity to establish an appropriate pre-treatment approach for MWCNTs in order to fully utilize the beneficial transport properties of this material in mixed matrix polymer nanocomposite for gas separation. Copyright © 2012 Elsevier Inc. All rights reserved.

Paclitaxel solubility in aqueous dispersions and mixed micellar solutions of lecithin.

PubMed

Sznitowska, Malgorzata; Klunder, Malgorzata; Placzek, Marcin

2008-01-01

The aim of this study was to find a biocompatible, lecithin-based carrier for paclitaxel (PTX) suitable for intravenous infusion and ensuring a soluble PTX concentration of 100 mg/100 ml or higher for at least 24 h. Aqueous dispersions of egg or soya lecithin (water-lecithin dispersions, WLD), mixed micellar (MM) solutions of egg lecithin and sodium deoxycholate, and formulations containing lecithin plus the co-surfactants and co-solvents poloxamer, polysorbate, Span, benzalkonium chloride, and macrogol were investigated. Amorphous PTX was prepared by lyophilization. PTX co-lyophilized with surfactants was also studied. Unlike crystalline PTX, the drug in an amorphous form is easily soluble in 1-5% (w/w) WLD or in MM. The highest solubility (up to 570 mg/100 ml) was achieved in 5% WLD. Dissolved PTX precipitated from all tested formulations over 24 h. Despite this, concentrations of dissolved PTX of 100 mg/100 ml or higher were observed after 24 h in 5% egg WLD, 1-5% soya WLD, and in 5% MM (lecithin : deoxycholate ratio 1 : 1 w/w). When four different batches of 5% egg WLD were prepared, containing PTX in clinically relevant concentration of 100 mg/100 ml, no precipitation of PTX was observed within 24 h and this formulation is the most promising candidate for further in vivo studies. Neither additional surfactants nor co-lyophilization increased PTX solubility in the lecithin-based carriers. The use of parenteral emulsions as solvents for the co-lyophilized PTX also failed to increase the solubility of the drug up to the target concentration.

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.

Availability of ferric iron for microbial reduction in bottom sediments of the freshwater tidal potomac river.

PubMed

Lovley, D R; Phillips, E J

1986-10-01

The distribution of Fe(III), its availability for microbial reduction, and factors controlling Fe(III) availability were investigated in sediments from a freshwater site in the Potomac River Estuary. Fe(III) reduction in sediments incubated under anaerobic conditions and depth profiles of oxalate-extractable Fe(III) indicated that Fe(III) reduction was limited to depths of 4 cm or less, with the most intense Fe(III) reduction in the top 1 cm. In incubations of the upper 4 cm of the sediments, Fe(III) reduction was as important as methane production as a pathway for anaerobic electron flow because of the high rates of Fe(III) reduction in the 0- to 0.5-cm interval. Most of the oxalate-extractable Fe(III) in the sediments was not reduced and persisted to a depth of at least 20 cm. The incomplete reduction was not the result of a lack of suitable electron donors. The oxalate-extractable Fe(III) that was preserved in the sediments was considered to be in a form other than amorphous Fe(III) oxyhydroxide, since synthetic amorphous Fe(III) oxyhydroxide, amorphous Fe(III) oxyhydroxide adsorbed onto clay, and amorphous Fe(III) oxyhydroxide saturated with adsorbed phosphate or fulvic acids were all readily reduced. Fe(3)O(4) and the mixed Fe(III)-Fe(II) compound(s) that were produced during the reduction of amorphous Fe(III) oxyhydroxide in an enrichment culture were oxalate extractable but were not reduced, suggesting that mixed Fe(III)-Fe(II) compounds might account for the persistence of oxalate-extractable Fe(III) in the sediments. The availability of microbially reducible Fe(III) in surficial sediments demonstrates that microbial Fe(III) reduction can be important to organic matter decomposition and iron geochemistry. However, the overall extent of microbial Fe(III) reduction is governed by the inability of microorganisms to reduce most of the Fe(III) in the sediment.

Amorphous Mixed-Metal Oxide Thin Films from Aqueous Solution Precursors with Near-Atomic Smoothness.

PubMed

Kast, Matthew G; Cochran, Elizabeth A; Enman, Lisa J; Mitchson, Gavin; Ditto, Jeffrey; Siefe, Chris; Plassmeyer, Paul N; Greenaway, Ann L; Johnson, David C; Page, Catherine J; Boettcher, Shannon W

2016-12-28

Thin films with tunable and homogeneous composition are required for many applications. We report the synthesis and characterization of a new class of compositionally homogeneous thin films that are amorphous solid solutions of Al 2 O 3 and transition metal oxides (TMO x ) including VO x , CrO x , MnO x , Fe 2 O 3 , CoO x , NiO, CuO x , and ZnO. The synthesis is enabled by the rapid decomposition of molecular transition-metal nitrates TM(NO 3 ) x at low temperature along with precondensed oligomeric Al(OH) x (NO 3 ) 3-x cluster species, both of which can be processed from aq solution. The films are dense, ultrasmooth (R rms < 1 nm, near 0.1 nm in many cases), and atomically mixed amorphous metal-oxide alloys over a large composition range. We assess the chemical principles that favor the formation of amorphous homogeneous films over rougher phase-segregated nanocrystalline films. The synthesis is easily extended to other compositions of transition and main-group metal oxides. To demonstrate versatility, we synthesized amorphous V 0.1 Cr 0.1 Mn 0.1 Fe 0.1 Zn 0.1 Al 0.5 O x and V 0.2 Cr 0.2 Fe 0.2 Al 0.4 O x with R rms ≈ 0.1 nm and uniform composition. The combination of ideal physical properties (dense, smooth, uniform) and broad composition tunability provides a platform for film synthesis that can be used to study fundamental phenomena when the effects of transition metal cation identity, solid-state concentration of d-electrons or d-states, and/or crystallinity need to be controlled. The new platform has broad potential use in controlling interfacial phenomena such as electron transfer in solar-cell contacts or surface reactivity in heterogeneous catalysis.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

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

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Effect of Sb on physical properties and microstructures of laser nano/amorphous-composite film

NASA Astrophysics Data System (ADS)

Li, Jia-Ning; Gong, Shui-Li; Sun, Mei; Shan, Fei-Hu; Wang, Xi-Chang; Jiang, Shuai

2013-11-01

A nano/amorphous-composite film was fabricated by laser cladding (LC) of the Co-Ti-B4C-Sb mixed powders on a TA15 alloy. Such film mainly consisted of Ti-Al, Co-Ti, Co-Sb intermetallics, TiC, TiB2, TiB, and the amorphous phases. Experimental results indicated that the crystal systems of TiB2 (hexagonal)/TiC (cubic) and Sb (rhombohedral) played important role on the formation of such film. Due to the mismatch of these crystals systems and mutual immiscibility of the metallic components, Sb was not incorporated in TiB2/TiC, but formed separate nuclei during the film growth. Thus, the growth of TiB2/TiC was stopped by the Sb nucleus in such LC molten pool, so as to form the nanoscale particles.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

PubMed Central

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-01-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials. PMID:27803330

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

DOE PAGES

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; ...

2016-11-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

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

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.

Imprinting bulk amorphous alloy at room temperature

DOE PAGES

Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T.; ...

2015-11-13

We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the abilitymore » of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. In conclusion, our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment.« less

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

Protein aggregate turbidity: Simulation of turbidity profiles for mixed-aggregation reactions.

PubMed

Hall, Damien; Zhao, Ran; Dehlsen, Ian; Bloomfield, Nathaniel; Williams, Steven R; Arisaka, Fumio; Goto, Yuji; Carver, John A

2016-04-01

Due to their colloidal nature, all protein aggregates scatter light in the visible wavelength region when formed in aqueous solution. This phenomenon makes solution turbidity, a quantity proportional to the relative loss in forward intensity of scattered light, a convenient method for monitoring protein aggregation in biochemical assays. Although turbidity is often taken to be a linear descriptor of the progress of aggregation reactions, this assumption is usually made without performing the necessary checks to provide it with a firm underlying basis. In this article, we outline utilitarian methods for simulating the turbidity generated by homogeneous and mixed-protein aggregation reactions containing fibrous, amorphous, and crystalline structures. The approach is based on a combination of Rayleigh-Gans-Debye theory and approximate forms of the Mie scattering equations. Crown Copyright © 2015. Published by Elsevier Inc. All rights reserved.

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

Ultralow power continuous-wave frequency conversion in hydrogenated amorphous silicon waveguides.

PubMed

Wang, Ke-Yao; Foster, Amy C

2012-04-15

We demonstrate wavelength conversion through nonlinear parametric processes in hydrogenated amorphous silicon (a-Si:H) with maximum conversion efficiency of -13 dB at telecommunication data rates (10 GHz) using only 15 mW of pump peak power. Conversion bandwidths as large as 150 nm (20 THz) are measured in continuous-wave regime at telecommunication wavelengths. The nonlinear refractive index of the material is determined by four-wave mixing (FWM) to be n(2)=7.43×10(-13) cm(2)/W, approximately an order of magnitude larger than that of single crystal silicon. © 2012 Optical Society of America

Novel nanometer-level uniform amorphous carbon coating for boron powders by direct pyrolysis of coronene without solvent.

PubMed

Ye, ShuJun; Song, MingHui; Kumakura, Hiroaki

2015-01-30

A 3 nm coronene coating and a 4 nm amorphous carbon coating with a uniform shell-core encapsulation structure for nanosized boron (B) powders are formed by a simple process in which coronene is directly mixed with boron particles without a solvent and heated at 520 °C for 1 h or at 630 °C for 3 h in a vacuum-sealed silica tube. Coronene has a melting point lower than its decomposition temperature, which enables liquid coronene to cover B particles by liquid diffusion and penetration without the need for a solvent. The diffusion and penetration of coronene can extend to the boundaries of particles and to inside the agglomerated nanoparticles to form a complete shell-core encapsulated structure. As the temperature is increased, thermal decomposition of coronene on the B particles results in the formation of a uniform amorphous carbon coating layer. This novel and simple nanometer-level uniform amorphous carbon coating method can possibly be applied to many other powders; thus, it has potential applications in many fields at low cost.

Mixed-mode high-power impulse magnetron sputter deposition of tetrahedral amorphous carbon with pulse-length control of ionization

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

Tucker, M. D.; Marks, N. A.; Ganesan, R.

2016-04-21

High-power impulse magnetron sputtering (HiPIMS) is used to deposit amorphous carbon thin films with sp{sup 3} fractions of 13% to 82%. Increasing the pulse length results in a transition from conventional HiPIMS deposition to a “mixed-mode” in which an arc triggers on the target surface, resulting in a large flux of carbon ions. The films are characterized using X-ray photoelectron spectroscopy, Raman spectroscopy, ellipsometry, nanoindentation, elastic recoil detection analysis, and measurements of stress and contact angle. All properties vary in a consistent manner, showing a high tetrahedral character only for long pulses, demonstrating that mixed-mode deposition is the source ofmore » the high carbon ion flux. Varying the substrate bias reveals an “energy window” effect, where the sp{sup 3} fraction of the films is greatest for a substrate bias around −100 V and decreases for higher or lower bias values. In the absence of bias, the films' properties show little dependence on the pulse length, showing that energetic ions are the origin of the highly tetrahedral character.« less

Bacterial nanometric amorphous Fe-based oxide: a potential lithium-ion battery anode material.

PubMed

Hashimoto, Hideki; Kobayashi, Genki; Sakuma, Ryo; Fujii, Tatsuo; Hayashi, Naoaki; Suzuki, Tomoko; Kanno, Ryoji; Takano, Mikio; Takada, Jun

2014-04-23

Amorphous Fe(3+)-based oxide nanoparticles produced by Leptothrix ochracea, aquatic bacteria living worldwide, show a potential as an Fe(3+)/Fe(0) conversion anode material for lithium-ion batteries. The presence of minor components, Si and P, in the original nanoparticles leads to a specific electrode architecture with Fe-based electrochemical centers embedded in a Si, P-based amorphous matrix.

Production and Characterization of Bulk MgB2 Material made by the Combination of Crystalline and Carbon Coated Amorphous Boron Powders

NASA Astrophysics Data System (ADS)

Hiroki, K.; Muralidhar, M.; Koblischka, M. R.; Murakami, M.

2017-07-01

The object of this investigation is to reduce the cost of bulk production and in the same time to increase the critical current performance of bulk MgB2 material. High-purity commercial powders of Mg metal (99.9% purity) and two types of crystalline (99% purity) and 16.5 wt% carbon-coated, nanometer-sized amorphous boron powders (98.5% purity) were mixed in a nominal composition of MgB2 to reduce the boron cost and to see the effect on the superconducting and magnetic properties. Several samples were produced mixing the crystalline boron and carbon-coated, nanometer-sized amorphous boron powders in varying ratios (50:50, 60:40, 70:30, 80:20, 90:10) and synthesized using a single-step process using the solid state reaction around 800 °C for 3 h in pure argon atmosphere. The magnetization measurements exhibited a sharp superconducting transition temperature with T c, onset around 38.6 K to 37.2 K for the bulk samples prepared utilizing the mixture of crystalline boron and 16.5% carbon-coated amorphous boron. The critical current density at higher magnetic field was improved with addition of carbon-coated boron to crystalline boron in a ratio of 80:20. The highest self-field Jc around 215,000 A/cm2 and 37,000 A/cm2 were recorded at 20 K, self-field and 2 T for the sample with a ratio of 80:10. The present results clearly demonstrate that the bulk MgB2 performance can be improved by adding carbon-coated nano boron to crystalline boron, which will be attractive to reduce the cost of bulk MgB2 material for several industrial applications.

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.

Use of X-ray diffraction to quantify amorphous supplementary cementitious materials in anhydrous and hydrated blended cements

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

Snellings, R., E-mail: ruben.snellings@epfl.ch; Salze, A.; Scrivener, K.L., E-mail: karen.scrivener@epfl.ch

2014-10-15

The content of individual amorphous supplementary cementitious materials (SCMs) in anhydrous and hydrated blended cements was quantified by the PONKCS [1] X-ray diffraction (XRD) method. The analytical precision and accuracy of the method were assessed through comparison to a series of mixes of known phase composition and of increasing complexity. A 2σ precision smaller than 2–3 wt.% and an accuracy better than 2 wt.% were achieved for SCMs in mixes with quartz, anhydrous Portland cement, and hydrated Portland cement. The extent of reaction of SCMs in hydrating binders measured by XRD was 1) internally consistent as confirmed through the standardmore » addition method and 2) showed a linear correlation to the cumulative heat release as measured independently by isothermal conduction calorimetry. The advantages, limitations and applicability of the method are discussed with reference to existing methods that measure the degree of reaction of SCMs in blended cements.« less

Oxidative Dissolution of Arsenopyrite by Mesophilic and Moderately Thermophilic Acidophiles †

PubMed Central

Tuovinen, Olli H.; Bhatti, Tariq M.; Bigham, Jerry M.; Hallberg, Kevin B.; Garcia, Oswaldo; Lindström, E. Börje

1994-01-01

The purpose of this work was to determine solution- and solid-phase changes associated with the oxidative leaching of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans and a moderately thermoacidophilic mixed culture. Jarosite [KFe3(SO4)2(OH)6], elemental sulfur (S0), and amorphous ferric arsenate were detected by X-ray diffraction as solid-phase products. The oxidation was not a strongly acid-producing reaction and was accompanied by a relatively low redox level. The X-ray diffraction lines of jarosite increased considerably when ferrous sulfate was used as an additional substrate for T. ferroxidans. A moderately thermoacidophilic mixed culture oxidized arsenopyrite faster at 45°C than did T. ferroxidans at 22°C, and the oxidation was accompanied by a nearly stoichiometric release of Fe and As. The redox potential was initially low but subsequently increased during arsenopyrite oxidation by the thermoacidophiles. Jarosite, S0, and amorphous ferric arsenate were also formed under these conditions. PMID:16349379

Method for continuous synthesis of metal oxide powders

DOEpatents

Berry, David A.; Haynes, Daniel J.; Shekhawat, Dushyant; Smith, Mark W.

2015-09-08

A method for the rapid and continuous production of crystalline mixed-metal oxides from a precursor solution comprised of a polymerizing agent, chelated metal ions, and a solvent. The method discharges solution droplets of less than 500 .mu.m diameter using an atomizing or spray-type process into a reactor having multiple temperature zones. Rapid evaporation occurs in a first zone, followed by mixed-metal organic foam formation in a second zone, followed by amorphous and partially crystalline oxide precursor formation in a third zone, followed by formation of the substantially crystalline mixed-metal oxide in a fourth zone. The method operates in a continuous rather than batch manner and the use of small droplets as the starting material for the temperature-based process allows relatively high temperature processing. In a particular embodiment, the first zone operates at 100-300.degree. C., the second zone operates at 300-700.degree. C., and the third operates at 700-1000.degree. C., and fourth zone operates at at least 700.degree. C. The resulting crystalline mixed-metal oxides display a high degree of crystallinity and sphericity with typical diameters on the order of 50 .mu.m or less.

Evaluation of Amorphous Transformer by Optimum Capacity Selection based on the Load Curve Pattern of Customers

NASA Astrophysics Data System (ADS)

Takagi, Masaaki; Yamamoto, Hiromi; Yamaji, Kenji

Energy loss in transformer is composed of no-load loss and load loss. No-load loss of amorphous transformer (i.e. amorphous metal-based transformer) is less by about 70% compared with traditional transformers (e.g. silicon steel-based transformer). However, amorphous transformers have disadvantages of high cost and high load loss parameter compared with traditional transformers. Furthermore, there are varieties of transformer capacities, and the customers who would buy new transformer have many choices. In this paper, the authors propose an algorithm for optimum transformer selection based on the load curve patterns of customers. It is possible to select the capacity that minimizes the total cost by measuring equivalent load Qe that is the root mean square of load. It becomes clear that amorphous transformer is effective in achieving substantial energy saving compared with traditional transformer.

Hydrazine-Assisted Formation of Indium Phosphide (InP)-Based Nanowires and Core-Shell Composites

PubMed Central

Patzke, Greta R.; Kontic, Roman; Shiolashvili, Zeinab; Makhatadze, Nino; Jishiashvili, David

2012-01-01

Indium phosphide nanowires (InP NWs) are accessible at 440 °C from a novel vapor phase deposition approach from crystalline InP sources in hydrazine atmospheres containing 3 mol % H2O. Uniform zinc blende (ZB) InP NWs with diameters around 20 nm and lengths up to several tens of micrometers are preferably deposited on Si substrates. InP particle sizes further increase with the deposition temperature. The straightforward protocol was extended on the one-step formation of new core-shell InP–Ga NWs from mixed InP/Ga source materials. Composite nanocables with diameters below 20 nm and shells of amorphous gallium oxide are obtained at low deposition temperatures around 350 °C. Furthermore, InP/Zn sources afford InP NWs with amorphous Zn/P/O-coatings at slightly higher temperatures (400 °C) from analogous setups. At 450 °C, the smooth outer layer of InP-Zn NWs is transformed into bead-shaped coatings. The novel combinations of the key semiconductor InP with isotropic insulator shell materials open up interesting application perspectives in nanoelectronics. PMID:28809296

Si-H bond dynamics in hydrogenated amorphous silicon

NASA Astrophysics Data System (ADS)

Scharff, R. Jason; McGrane, Shawn D.

2007-08-01

The ultrafast structural dynamics of the Si-H bond in the rigid solvent environment of an amorphous silicon thin film is investigated using two-dimensional infrared four-wave mixing techniques. The two-dimensional infrared (2DIR) vibrational correlation spectrum resolves the homogeneous line shapes ( <2.5cm-1 linewidth) of the 0→1 and 1→2 vibrational transitions within the extensively inhomogeneously broadened ( 78cm-1 linewidth) Si-H vibrational band. There is no spectral diffusion evident in correlation spectra obtained at 0.2, 1, and 4ps waiting times. The Si-H stretching mode anharmonic shift is determined to be 84cm-1 and decreases slightly with vibrational frequency. The 1→2 linewidth increases with vibrational frequency. Frequency dependent vibrational population times measured by transient grating spectroscopy are also reported. The narrow homogeneous line shape, large inhomogeneous broadening, and lack of spectral diffusion reported here present the ideal backdrop for using a 2DIR probe following electronic pumping to measure the transient structural dynamics implicated in the Staebler-Wronski degradation [Appl. Phys. Lett. 31, 292 (1977)] in a-Si:H based solar cells.

Hydrazine-Assisted Formation of Indium Phosphide (InP)-Based Nanowires and Core-Shell Composites.

PubMed

Patzke, Greta R; Kontic, Roman; Shiolashvili, Zeinab; Makhatadze, Nino; Jishiashvili, David

2012-12-27

Indium phosphide nanowires (InP NWs) are accessible at 440 °C from a novel vapor phase deposition approach from crystalline InP sources in hydrazine atmospheres containing 3 mol % H₂O. Uniform zinc blende (ZB) InP NWs with diameters around 20 nm and lengths up to several tens of micrometers are preferably deposited on Si substrates. InP particle sizes further increase with the deposition temperature. The straightforward protocol was extended on the one-step formation of new core-shell InP-Ga NWs from mixed InP/Ga source materials. Composite nanocables with diameters below 20 nm and shells of amorphous gallium oxide are obtained at low deposition temperatures around 350 °C. Furthermore, InP/Zn sources afford InP NWs with amorphous Zn/P/O-coatings at slightly higher temperatures (400 °C) from analogous setups. At 450 °C, the smooth outer layer of InP-Zn NWs is transformed into bead-shaped coatings. The novel combinations of the key semiconductor InP with isotropic insulator shell materials open up interesting application perspectives in nanoelectronics.

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.

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.

Classification of the crystallization behavior of amorphous active pharmaceutical ingredients in aqueous environments.

PubMed

Van Eerdenbrugh, Bernard; Raina, Shweta; Hsieh, Yi-Ling; Augustijns, Patrick; Taylor, Lynne S

2014-04-01

To classify the crystallization behavior of amorphous active pharmaceutical ingredients (API) exposed to aqueous environments. A set of approximately 50 chemically and physically diverse active pharmaceutical ingredients (APIs) was selected for this study. Two experimental setups were employed to characterize the crystallization behavior of the amorphous API in an aqueous environment. For the first approach, precipitation, as evidenced by the development of turbidity, was induced using the solvent shift method, by mixing concentrated API solutions in DMSO with an aqueous buffer in a capillary. Subsequently, crystallization was monitored in situ over time using synchrotron radiation (simultaneous SAXS/WAXS beamline 12-ID-B at the Advanced Photon Source, Argonne National Laboratories, Argonne, IL). In the second approach, amorphous films were prepared by melt quenching; after adding buffer, crystallization was monitored with time using polarized light microscopy. In general, the crystallization behavior of a given compound was similar irrespective of the experimental method employed. However, the crystallization behavior among different compounds varied significantly, ranging from immediate and complete crystallization to no observable crystallization over biorelevant time scales. Comparison of the observed behavior with previous studies of crystallization tendency in non-aqueous environments revealed that the crystallization tendency of individual APIs was somewhat similar regardless of the crystallization environment. API properties, rather than the method by which amorphous materials are generated, tend to dictate crystallization behavior in aqueous media.

Different structural morphologies of the two surfaces in some Co-based amorphous ribbons

NASA Astrophysics Data System (ADS)

Bordin, G.; Buttino, G.

1992-12-01

In nearly zero magnetostriction Co-based Metglas amorphous ribbons, the anomalous Hall effect is used to investigate the behaviour of the surfaces (dull or shiny). The electronic transport properties of a double-layer film, where one of the two layers examined is ferromagnetic and amorphous, and the other is a non-magnetic film, are interpreted on the basis of the mean free path method of Bergmann and Fuchs-Sondheimer theory. The results obtained confirm the different structural morphology of the amorphous surfaces (dull or shiny) already observed by means of bending effects on the initial permeability that depends on the way of winding the ribbons in toroidal samples of the same amorphous materials.

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.

Minor-Cu doped soft magnetic Fe-based FeCoBCSiCu amorphous alloys with high saturation magnetization

NASA Astrophysics Data System (ADS)

Li, Yanhui; Wang, Zhenmin; Zhang, Wei

2018-05-01

The effects of Cu alloying on the amorphous-forming ability (AFA) and magnetic properties of the P-free Fe81Co5B11C2Si1 amorphous alloy were investigated. Addition of ≤ 1.0 at.% Cu enhances the AFA of the base alloy without significant deterioration of the soft magnetic properties. The Fe80.5Co5B11C2Si1Cu0.5 alloy with the largest critical thickness for amorphous formation of ˜35 μm possesses a high saturation magnetization (Bs) of ˜1.78 T, low coercivity of ˜14.6 A/m, and good bending ductility upon annealing in a wide temperature range of 513-553 K with maintaining the amorphous state. The fabrication of the new high-Fe-content Fe-Co-B-C-Si-Cu amorphous alloys by minor doping of Cu gives a guideline to developing high Bs amorphous alloys with excellent AFA.

Molecular blends of methylated-poly(ethylenimine) and amorphous porous organic cages for SO 2 adsorption

DOE PAGES

Zhu, Guanghui; Carrillo, Jan-Michael Y.; Sujan, Achintya; ...

2018-01-01

Porous organic cage (POCs) are explored as a support for hazardous gas sorbents. The molecular mixing between the POC and methylated poly(ethylene imine) was observed and resulted in the improvement of mass transfer and thermal stability of the composite material.

Mixed anion materials and compounds for novel proton conducting membranes

DOEpatents

Poling, Steven Andrew; Nelson, Carly R.; Martin, Steve W.

2006-09-05

The present invention provides new amorphous or partially crystalline mixed anion chalcogenide compounds for use in proton exchange membranes which are able to operate over a wide variety of temperature ranges, including in the intermediate temperature range of about 100 .degree. C. to 300.degree. C., and new uses for crystalline mixed anion chalcogenide compounds in such proton exchange membranes. In one embodiment, the proton conductivity of the compounds is between about 10.sup.-8 S/cm and 10.sup.-1 S/cm within a temperature range of between about -60 and 300.degree. C. and a relative humidity of less than about 12%..

Mechanism of amorphisation of micro-particles of griseofulvin during powder flow in a mixer.

PubMed

Pazesh, Samaneh; Höckerfelt, Mina Heidarian; Berggren, Jonas; Bramer, Tobias; Alderborn, Göran

2013-11-01

The purpose of the research was to investigate the degree of solid-state amorphisation during powder flow and to propose a mechanism for this transformation. Micro-particles of griseofulvin (about 2 μm in diameter) were mixed in a shear mixer under different conditions to influence the inter-particulate collisions during flow, and the degree of amorphisation was determined by micro-calorimeter. The amorphisation of griseofulvin particles (GPs) during repeated compaction was also determined. The GPs generally became disordered during mixing in a range from about 6% to about 86%. The degree of amorphisation increased with increased mixing time and increased batch size of the mixer, whereas the addition of a lubricant to the blend reduced the degree of amorphisation. Repeated compaction using the press with ejection mode gave limited amorphisation, whereas repeated compaction without an ejection process gave minute amorphisation. It is concluded that during powder flow, the most important inter-particulate contact process that cause the transformation of a crystalline solid into an amorphous state is sliding. On the molecular scale, this amorphisation is proposed to be caused by vitrification, that is the melting of a solid because of the generation of heat during sliding followed by solidification into an amorphous phase. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Amorphous silicon carbide passivating layers for crystalline-silicon-based heterojunction solar cells

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

Boccard, Mathieu; Holman, Zachary C.

Amorphous silicon enables the fabrication of very high-efficiency crystalline-silicon-based solar cells due to its combination of excellent passivation of the crystalline silicon surface and permeability to electrical charges. Yet, amongst other limitations, the passivation it provides degrades upon high-temperature processes, limiting possible post-deposition fabrication possibilities (e.g., forcing the use of low-temperature silver pastes). We investigate the potential use of intrinsic amorphous silicon carbide passivating layers to sidestep this issue. The passivation obtained using device-relevant stacks of intrinsic amorphous silicon carbide with various carbon contents and doped amorphous silicon are evaluated, and their stability upon annealing assessed, amorphous silicon carbide beingmore » shown to surpass amorphous silicon for temperatures above 300 °C. We demonstrate open-circuit voltage values over 700 mV for complete cells, and an improved temperature stability for the open-circuit voltage. Transport of electrons and holes across the hetero-interface is studied with complete cells having amorphous silicon carbide either on the hole-extracting side or on the electron-extracting side, and a better transport of holes than of electrons is shown. Also, due to slightly improved transparency, complete solar cells using an amorphous silicon carbide passivation layer on the hole-collecting side are demonstrated to show slightly better performances even prior to annealing than obtained with a standard amorphous silicon layer.« less

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

Magnesium-Aluminum-Zirconium Oxide Amorphous Ternary Composite: A Dense and Stable Optical Coating

NASA Technical Reports Server (NTRS)

Sahoo, N. K.; Shapiro, A. P.

1998-01-01

In the present work, the process parameter dependent optical and structural properties of MgO-Al(2)O(3)-ZrO(2) ternary mixed-composite material have been investigated. Optical properties were derived from spectrophotometric measurements. The surface morphology, grain size distributions, crystallographic phases and process dependent material composition of films have been investigated through the use of Atomic Force Microscopy (AFM), X-ray diffraction analysis and Energy Dispersive X- ray (EDX) analysis. EDX analysis made evident the correlation between the optical constants and the process dependent compositions in the films. It is possible to achieve environmentally stable amorphous films with high packing density under certain optimized process conditions.

MgO-Al2O3-ZrO2 Amorphous Ternary Composite: A Dense and Stable Optical Coating

NASA Technical Reports Server (NTRS)

Shaoo, Naba K.; Shapiro, Alan P.

1998-01-01

The process-parameter-dependent optical and structural properties of MgO-Al2O3-ZrO2 ternary mixed-composite material were investigated. Optical properties were derived from spectrophotometric measurements. The surface morphology, grain size distributions, crystallographic phases, and process- dependent material composition of films were investigated through the use of atomic force microscopy, x-ray diffraction analysis, and energy-dispersive x-ray analysis. Energy-dispersive x-ray analysis made evident the correlation between the optical constants and the process-dependent compositions in the films. It is possible to achieve environmentally stable amorphous films with high packing density under certain optimized process conditions.

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.;

Investigation of phase stability of novel equiatomic FeCoNiCuZn based-high entropy alloy prepared by mechanical alloying

NASA Astrophysics Data System (ADS)

Soni, Vinay Kumar; Sanyal, S.; Sinha, S. K.

2018-05-01

The present work reports the structural and phase stability analysis of equiatomic FeCoNiCuZn High entropy alloy (HEA) systems prepared by mechanical alloying (MA) method. In this research effort some 1287 alloy combinations were extensively studied to arrive at most favourable combination. FeCoNiCuZn based alloy system was selected on the basis of physiochemical parameters such as enthalpy of mixing (ΔHmix), entropy of mixing (ΔSmix), atomic size difference (ΔX) and valence electron concentration (VEC) such that it fulfils the formation criteria of stable multi component high entropy alloy system. In this context, we have investigated the effect of novel alloying addition in view of microstructure and phase formation aspect. XRD plots of the MA samples shows the formation of stable solid solution with FCC (Face Cantered Cubic) after 20 hr of milling time and no indication of any amorphous or intermetallic phase formation. Our results are in good agreement with calculation and analysis done on the basis of physiochemical parameters during selection of constituent elements of HEA.

Additive Mixing and Conformal Coating of Noniridescent Structural Colors with Robust Mechanical Properties Fabricated by Atomization Deposition.

PubMed

Li, Qingsong; Zhang, Yafeng; Shi, Lei; Qiu, Huihui; Zhang, Suming; Qi, Ning; Hu, Jianchen; Yuan, Wei; Zhang, Xiaohua; Zhang, Ke-Qin

2018-04-24

Artificial structural colors based on short-range-ordered amorphous photonic structures (APSs) have attracted great scientific and industrial interest in recent years. However, the previously reported methods of self-assembling colloidal nanoparticles lack fine control of the APS coating and fixation on substrates and poorly realize three-dimensional (3D) conformal coatings for objects with irregular or highly curved surfaces. In this paper, atomization deposition of silica colloidal nanoparticles with poly(vinyl alcohol) as the additive is proposed to solve the above problems. By finely controlling the thicknesses of APS coatings, additive mixing of noniridescent structural colors is easily realized. Based on the intrinsic omnidirectional feature of atomization, a one-step 3D homogeneous conformal coating is also readily realized on various irregular or highly curved surfaces, including papers, resins, metal plates, ceramics, and flexible silk fabrics. The vivid coatings on silk fabrics by atomization deposition possess robust mechanical properties, which are confirmed by rubbing and laundering tests, showing great potential in developing an environmentally friendly coloring technique in the textile industry.

Optimal Composite Material for Low Cost Fabrication of Large Composite Aerospace Structures using NASA Resins or POSS Nanoparticle Modifications

NASA Technical Reports Server (NTRS)

Lamontia, Mark A.; Gruber, Mark B.; Jensen, Brian J.

2006-01-01

Thermoplastic laminates in situ consolidated via tape or tow placement require full mechanical properties. Realizing full properties requires resin crystallinity to be controlled - partial crystallinity leads to unacceptably low laminate compression properties. There are two approaches: utilize an amorphous matrix resin; or place material made from a semi-crystalline resin featuring kinetics faster than the process. In this paper, a matrix resin evaluation and trade study was completed with commercial and NASA amorphous polyimides on the one hand, and with PEKK mixed with POSS nanoparticles for accelerated crystallinity growth on the other. A new thermoplastic impregnated material, 6 mm wide (0.25-in) AS-4 carbon/LaRC(TradeMark)8515 dry polyimide tow, was fabricated. Since LaRC(TradeMark)8515 is fully amorphous, it attains full properties following in situ consolidation, with no post processing required to build crystallinity. The tow in situ processing was demonstrated via in situ thermoplastic filament winding it into rings.

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.

Natural realgar and amorphous AsS oxidation kinetics

NASA Astrophysics Data System (ADS)

Lengke, Maggy F.; Tempel, Regina N.

2003-03-01

The oxidation rates of natural realgar and amorphous synthetic AsS by dissolved oxygen were evaluated using mixed flow reactors at pH 7.2 to 8.8 and dissolved oxygen contents of 5.9 to 16.5 ppm over a temperature range of 25 to 40°C. The ratios of As/S are stoichiometric for all amorphous AsS oxidation experiments except for two experiments conducted at pH ˜8.8. In these experiments, stoichiometric ratios of As/S were only observed in the early stages of AsS (am) oxidation whereas lower As/S ratios were observed during steady state. For realgar oxidation experiments, the As/S ratio is less than the stoichiometric ratio of realgar, ranging between 0.61 and 0.71. This nonstoichiometric release of As and S to solution indicates that realgar oxidation is more selective for S after the rates of oxidation become constant. All measured oxidation rates at 25°C can be described within experimental uncertainties as follows: Table 1

Compatibility of the totally replaced hip. Reduction of wear by amorphous diamond coating.

PubMed

Santavirta, Seppo

2003-12-01

Particulate wear debris in totally replaced hips causes adverse local host reactions. The extreme form of such a reaction, aggressive granulomatosis, was found to be a distinct condition and different from simple aseptic loosening. Reactive and adaptive tissues around the totally replaced hip were made of proliferation of local fibroblast like cells and activated macrophages. Methylmethacrylate and high-molecular-weight polyethylene were shown to be essentially immunologically inert implant materials, but in small particulate form functioned as cellular irritants initiating local biological reactions leading to loosening of the implants. Chromium-cobalt-molybdenum is the most popular metallic implant material; it is hard and tough, and the bearings of this metal are partially self-polishing. In total hip implants, prerequisites for longevity of the replaced hip are good biocompatibility of the materials and sufficient tribological properties of the bearings. The third key issue is that the bearing must minimize frictional shear at the prosthetic bone-implant interface to be compatible with long-term survival. Some of the approaches to meet these demands are alumina-on-alumina and metal-on-metal designs, as well as the use of highly crosslinked polyethylene for the acetabular component. In order to avoid the wear-based deleterious properties of the conventional total hip prosthesis materials or coatings, the present work included biological and tribological testing of amorphous diamond. Previous experiments had demonstrated that a high adhesion of tetrahedral amorphous carbon coatings to a substrate can be achieved by using mixing layers or interlayers. Amorphous diamond was found to be biologically inert, and simulator testing indicated excellent wear properties for conventional total hip prostheses, in which either the ball or both bearing surfaces were coated with hydrogen-free tetrahedral amorphous diamond films. Simulator testing with such total hip prostheses showed no measurable wear or detectable delamination after 15,000,000 test cycles corresponding to 15 years of clinical use. The present work clearly shows that wear is one of the basic problems with totally replaced hips. Diamond coating of the bearing surfaces appears to be an attractive solution to improve longevity of the totally replaced hip.

Structure and Properties of Sn2Se3, a mixed valent tin selenium compound

NASA Astrophysics Data System (ADS)

Xing, Guangzong; Li, Yuwei; Fan, Xiaofeng; Zhang, Lijun; Singh, David

Sn2Se3 is a possibly expected phase based on analogy with Sn2S3 but it has never been reported. It is of interest due to reported phase change memories using this composition using transitions between an amorphous phase and an unknown crystalline phase. We identify the crystal structure Sn2Se3 and report its properties at ambient pressure based on the ab initio evolutionary methodology for crystal structure prediction implemented in the Calypso code. We find a structure based on Sn-Se ribbons with clear Sn(II)and Sn(IV)sites similar to the structure of Sn2S3. Compared with the known phase SnSe (Pnma) +SnSe2 (P-3m1), the energy is only 2.3meV/atom higher. The electronic structure of this phase shows mixed valent tins Sn2+ and Sn4+ in this compound. A small band gap of 0.023 eV is obtained from the band structure consistent with the small resistance reported by Kyung-Min Chung et al. Work at the University of Missouri is supported by DOE through the S3TEC EFRC.

Secondary growth mechanism of SiGe islands deposited on a mixed-phase microcrystalline Si by ion beam co-sputtering.

PubMed

Ke, S Y; Yang, J; Qiu, F; Wang, Z Q; Wang, C; Yang, Y

2015-11-06

We discuss the SiGe island co-sputtering deposition on a microcrystalline silicon (μc-Si) buffer layer and the secondary island growth based on this pre-SiGe island layer. The growth phenomenon of SiGe islands on crystalline silicon (c-Si) is also investigated for comparison. The pre-SiGe layer grown on μc-Si exhibits a mixed-phase structure, including SiGe islands and amorphous SiGe (a-SiGe) alloy, while the layer deposited on c-Si shows a single-phase island structure. The preferential growth and Ostwald ripening growth are shown to be the secondary growth mechanism of SiGe islands on μc-Si and c-Si, respectively. This difference may result from the effect of amorphous phase Si (AP-Si) in μc-Si on the island growth. In addition, the Si-Ge intermixing behavior of the secondary-grown islands on μc-Si is interpreted by constructing the model of lateral atomic migration, while this behavior on c-Si is ascribed to traditional uphill atomic diffusion. It is found that the aspect ratios of the preferential-grown super islands are higher than those of the Ostwald-ripening ones. The lower lateral growth rate of super islands due to the lower surface energy of AP-Si on the μc-Si buffer layer for the non-wetting of Ge at 700 °C and the stronger Si-Ge intermixing effect at 730 °C may be responsible for this aspect ratio difference.

Effects of the addition of Co, Ni or Cr on the decolorization properties of Fe-Si-B amorphous alloys

NASA Astrophysics Data System (ADS)

Zhang, Changqin; Zhu, Zhengwang; Zhang, Haifeng

2017-11-01

Fe-based amorphous alloys show great potential in degrading azo dyes and other organic pollutants, and are widely investigated as a kind of environmental-friendly materials for wastewater remediation. In this paper, the effects of Co, Ni or Cr addition on the decolorization properties of Fe-Si-B amorphous alloys were studied, and the mechanism of their different effects was analyzed. Co addition could lower the activation energy of Fe-Si-B amorphous alloys in decolorizing azo dyes, and had no weakening effect on the decolorization capability of Fe-Si-B amorphous alloys. Ni addition led to partial crystallization of Fe-Si-B amorphous alloys, and the decolorization mechanism at low temperatures changed from chemical degradation to physical adsorption. Cr addition could enhance the corrosion resistance of Fe-Si-B amorphous alloys, but the amorphous alloys completely lost the decolorization capability no matter at lower or higher temperatures. The results of X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) indicated that the addition of Co, Ni or Cr could generate different surface structures that had significant influences on the decolorization process. Our work demonstrated that the effiecient decolorization of azo dyes by Fe-based alloys could be realized only when amorphous nature and incompact surface structure were simultaneously achieved for the alloys.

Amorphous silicon carbide passivating layers for crystalline-silicon-based heterojunction solar cells

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

Boccard, Mathieu; Holman, Zachary C.

With this study, amorphous silicon enables the fabrication of very high-efficiency crystalline-silicon-based solar cells due to its combination of excellent passivation of the crystalline silicon surface and permeability to electrical charges. Yet, amongst other limitations, the passivation it provides degrades upon high-temperature processes, limiting possible post-deposition fabrication possibilities (e.g., forcing the use of low-temperature silver pastes). We investigate the potential use of intrinsic amorphous silicon carbide passivating layers to sidestep this issue. The passivation obtained using device-relevant stacks of intrinsic amorphous silicon carbide with various carbon contents and doped amorphous silicon are evaluated, and their stability upon annealing assessed, amorphousmore » silicon carbide being shown to surpass amorphous silicon for temperatures above 300°C. We demonstrate open-circuit voltage values over 700 mV for complete cells, and an improved temperature stability for the open-circuit voltage. Transport of electrons and holes across the hetero-interface is studied with complete cells having amorphous silicon carbide either on the hole-extracting side or on the electron-extracting side, and a better transport of holes than of electrons is shown. Also, due to slightly improved transparency, complete solar cells using an amorphous silicon carbide passivation layer on the hole-collecting side are demonstrated to show slightly better performances even prior to annealing than obtained with a standard amorphous silicon layer.« less

Amorphous silicon carbide passivating layers for crystalline-silicon-based heterojunction solar cells

DOE PAGES

Boccard, Mathieu; Holman, Zachary C.

2015-08-14

With this study, amorphous silicon enables the fabrication of very high-efficiency crystalline-silicon-based solar cells due to its combination of excellent passivation of the crystalline silicon surface and permeability to electrical charges. Yet, amongst other limitations, the passivation it provides degrades upon high-temperature processes, limiting possible post-deposition fabrication possibilities (e.g., forcing the use of low-temperature silver pastes). We investigate the potential use of intrinsic amorphous silicon carbide passivating layers to sidestep this issue. The passivation obtained using device-relevant stacks of intrinsic amorphous silicon carbide with various carbon contents and doped amorphous silicon are evaluated, and their stability upon annealing assessed, amorphousmore » silicon carbide being shown to surpass amorphous silicon for temperatures above 300°C. We demonstrate open-circuit voltage values over 700 mV for complete cells, and an improved temperature stability for the open-circuit voltage. Transport of electrons and holes across the hetero-interface is studied with complete cells having amorphous silicon carbide either on the hole-extracting side or on the electron-extracting side, and a better transport of holes than of electrons is shown. Also, due to slightly improved transparency, complete solar cells using an amorphous silicon carbide passivation layer on the hole-collecting side are demonstrated to show slightly better performances even prior to annealing than obtained with a standard amorphous silicon layer.« less

Evaluation of the Crystallization Tendency of Commercially Available Amorphous Tacrolimus Formulations Exposed to Different Stress Conditions.

PubMed

Trasi, Niraj S; Purohit, Hitesh S; Taylor, Lynne S

2017-10-01

Tacrolimus, an immunosuppressant, is a poorly water soluble compound whereby the commercially available capsule formulations contain the drug in amorphous form. The goal of this study was to evaluate the robustness of the innovator product and five generic formulations to crystallization following storage at stress conditions. Products were purchased from a pharmacy and stored at 40°C/75% relative humidity (RH), open dish conditions. Crystallinity was determined using X-ray diffraction. The quantity of the ingredients in the formulations were determined using different approaches and the various factors that might cause instability in the formulations were studied. After 4 weeks of open dish storage at 40°C/75% RH, one of the generic formulations showed evidence of tacrolimus crystallization. Further investigations revealed batch-to-batch variations in crystallization tendency with the extent of crystallinity varying between 50 and 100% for different batches. Crystallization was also observed at lower storage temperatures (30°C) when the RH was maintained at 75%. It was found that crystallization could be induced in a model formulation by wet granulating an ethanolic solution of the drug with lactose and drying at 60-70°C followed by exposure to stress conditions. It seems probable that the generic that was susceptible to crystallization contains amorphous drug physically mixed with polymeric excipients, rather than as an amorphous solid dispersion. This study highlights the importance of considering the manufacturing process on the stability of the resultant amorphous product.

Using Flory-Huggins phase diagrams as a pre-formulation tool for the production of amorphous solid dispersions: a comparison between hot-melt extrusion and spray drying.

PubMed

Tian, Yiwei; Caron, Vincent; Jones, David S; Healy, Anne-Marie; Andrews, Gavin P

2014-02-01

Amorphous drug forms provide a useful method of enhancing the dissolution performance of poorly water-soluble drugs; however, they are inherently unstable. In this article, we have used Flory-Huggins theory to predict drug solubility and miscibility in polymer candidates, and used this information to compare spray drying and melt extrusion as processes to manufacture solid dispersions. Solid dispersions were prepared using two different techniques (hot-melt extrusion and spray drying), and characterised using a combination of thermal (thermogravimetric analysis and differential scanning calorimetry), spectroscopic (Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction methods. Spray drying permitted generation of amorphous solid dispersions across a wider drug concentration than melt extrusion. Melt extrusion provided sufficient energy for more intimate mixing to be achieved between drug and polymer, which may improve physical stability. It was also confirmed that stronger drug-polymer interactions might be generated through melt extrusion. Remixing and dissolution of recrystallised felodipine into the polymeric matrices did occur during the modulated differential scanning calorimetry analysis, but the complementary information provided from FTIR confirms that all freshly prepared spray-dried samples were amorphous with the existence of amorphous drug domains within high drug-loaded samples. Using temperature-composition phase diagrams to probe the relevance of temperature and drug composition in specific polymer candidates facilitates polymer screening for the purpose of formulating solid dispersions. © 2013 Royal Pharmaceutical Society.

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.

Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater

NASA Astrophysics Data System (ADS)

Morris, Richard V.; Vaniman, David T.; Blake, David F.; Gellert, Ralf; Chipera, Steve J.; Rampe, Elizabeth B.; Ming, Douglas W.; Morrison, Shaunna M.; Downs, Robert T.; Treiman, Allan H.; Yen, Albert S.; Grotzinger, John P.; Achilles, Cherie N.; Bristow, Thomas F.; Crisp, Joy A.; Des Marais, David J.; Farmer, Jack D.; Fendrich, Kim V.; Frydenvang, Jens; Graff, Trevor G.; Morookian, John-Michael; Stolper, Edward M.; Schwenzer, Susanne P.

2016-06-01

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ˜40 wt.% crystalline and ˜60 wt.% X-ray amorphous material and a bulk composition with ˜74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (˜17 wt.% of bulk sample), tridymite (˜14 wt.%), sanidine (˜3 wt.%), cation-deficient magnetite (˜3 wt.%), cristobalite (˜2 wt.%), and anhydrite (˜1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (˜39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (˜5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin's tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.

Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Bish, D. L.; Chipera, S. J.; Morris, R. V.; Achilles, C. N.; Ming, D W.; Blake, D. F.; Anderson, R. C.; Bristow, T. F.; Crisp, A.;

Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater

PubMed Central

Morris, Richard V.; Vaniman, David T.; Blake, David F.; Gellert, Ralf; Chipera, Steve J.; Rampe, Elizabeth B.; Ming, Douglas W.; Morrison, Shaunna M.; Downs, Robert T.; Treiman, Allan H.; Yen, Albert S.; Grotzinger, John P.; Achilles, Cherie N.; Bristow, Thomas F.; Crisp, Joy A.; Des Marais, David J.; Farmer, Jack D.; Fendrich, Kim V.; Graff, Trevor G.; Morookian, John-Michael; Stolper, Edward M.; Schwenzer, Susanne P.

2016-01-01

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides−perchlorates−chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin’s tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill. PMID:27298370

Carbonate mineralization via an amorphous calcium carbonate (ACC) pathway: Tuning polymorph selection by Mg, pH, and mixing environment

NASA Astrophysics Data System (ADS)

Dove, P. M.; Blue, C.; Mergelsberg, S. T.; Giuffre, A. J.; Han, N.; De Yoreo, J. J.

2017-12-01

Mineral formation by nonclassical processes is widespread with many pathways that include aggregation of nanoparticles, oriented attachment of fully formed crystals, and sequential nucleation/transformation of amorphous phases (De Yoreo et al., 2015, Science). Field observations indicate amorphous calcium carbonate (ACC) can be the initial precipitate when local conditions promote high supersaturations for short time periods. Examples include microbial mats, marine porewaters that undergo pulses of increased alkalinity, closed basin lakes, and sabkhas. The crystalline products exhibit diverse morphologies and complex elemental and isotopic signatures. This study quantifies relationships between solution composition and the crystalline polymorphs that transform from ACC (Blue et al., GCA, 2017). Our experimental design synthesized ACC under controlled conditions for a suite of compositions by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within output suspensions under stirred or quiescent mixing while characterizing the polymorph and composition of evolving solutions and solids. We find that ACC transforms to crystalline polymorphs with a systematic relationship to solution composition to give a quantitative framework based upon solution aMg2+/aCa2+ and aCO32-/aCa2+. We also measure a polymorph-specific evolution of pH and Mg/Ca during the transformation that indicates the initial polymorph to form. Pathway is further modulated by stirring versus quiescent conditions. The findings reconcile discrepancies among previous studies of ACC to crystalline products and supports claims that monohydrocalcite may be an overlooked, transient phase during formation of some aragonite and calcite deposits. Organic additives and extreme pH are not required to tune composition and polymorph. Insights from this study reiterate the need to revisit long-standing dogmas regarding controls on CaCO3 polymorph selection. Classical models assume thermodynamic equilibria but cannot provide a reliable predictor of compositions when kinetic factors are driving mineralization. Nonclassical pathways to mineralization may be the missing link to interpreting unusual CaCO3 polymorphs, compositions and textures in modern and ancient carbonates.

Preparation and Optimization of Amorphous Ursodeoxycholic Acid Nano-suspensions by Nanoprecipitation based on Acid-base Neutralization for Enhanced Dissolution.

PubMed

Xie, Yike; Chen, Zhongjian; Su, Rui; Li, Ye; Qi, Jianping; Wu, Wei; Lu, Yi

2017-01-01

Ursodeoxycholic acid, usually used to dissolve cholesterol gallstones in clinic, is a typical hydrophobic drug with poor oral bioavailability due to dissolution rate-limited performance. The objective of this study was to increase the dissolution of ursodeoxycholic acid by amorphous nanosuspensions. Nanoprecipitation based on acid-base neutralization was used to prepare the nanosuspensions with central composite design to optimize the formula. The nanosuspensions were characterized by particle size, morphology, crystallology and dissolution. The ursodeoxycholic acid nanosuspensions showed mean particle size around 380 nm with polydispersion index value about 0.25. Scanning electron microscope observed high coverage of HPMC-E50 onto the surface of the nanosuspensions. Differential scanning calorimetry and powder X-ray diffractometry revealed amorphous structure of the ursodeoxycholic acid nanosuspensions. A significant increase of dissolution in acidic media was achieved by the amorphous nanosuspensions compared with the physical mixture. It can be predicted that the amorphous nanosuspensions show great potential in improving the oral bioavailability of ursodeoxycholic acid. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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.

Acoustic Emission Analysis of Damage during Compressive Deformation of Amorphous Zr-Based Foams with Aligned, Elongated Pores

NASA Astrophysics Data System (ADS)

Cox, Marie E.; Dunand, David C.

2013-07-01

Acoustic emission methods are used to investigate the evolution of internal microfractural damage during uniaxial compression of amorphous Zr-based foams with aligned, elongated pores. The foams are fabricated by means of densifying a blend of crystalline W powders and amorphous Zr-based powders with two oxygen contents (0.078 and 0.144 wt pct) by warm equal channel angular extrusion, followed by dissolution of the elongated W phase from the fully densified amorphous matrix. For the high-oxygen foams, prior powder boundaries in the amorphous struts promote damage that accumulates during compression, resulting in energy-absorbing properties comparable with the low-oxygen foams without stress-concentrating powder boundaries. The influence of pore orientation on the evolution of microfracture damage and the ability of the foams to accumulate damage without catastrophic failure is also investigated: pores oriented from 24 to 68 deg to the loading direction promote wall bending, resulting in foams with more diffuse damage and better energy-absorbing properties.

Localization of vibrational modes leads to reduced thermal conductivity of amorphous heterostructures

NASA Astrophysics Data System (ADS)

Giri, Ashutosh; Donovan, Brian F.; Hopkins, Patrick E.

2018-05-01

We investigate the vibrational heat transfer mechanisms in amorphous Stillinger-Weber silicon and germanium-based alloys and heterostructures via equilibrium and nonequilibrium molecular dynamics simulations along with lattice dynamics calculations. We find that similar to crystalline alloys, amorphous alloys demonstrate large size effects in thermal conductivity, while layering the constituent materials into superlattice structures leads to length-independent thermal conductivities. The thermal conductivity of an amorphous SixGe1 -x alloy reduces by as much as ˜53 % compared to the thermal conductivity of amorphous silicon; compared to the larger reduction in crystalline phases due to alloying, we show that compositional disorder rather than structural disorder has a larger impact on the thermal conductivity reduction. Our thermal conductivity predictions for a-Si/a-Ge superlattices suggest that the alloy limit in amorphous SiGe-based structures can be surpassed with interface densities above ˜0.35 nm-1 . We attribute the larger reduction in thermal conductivity of layered Si/Ge heterostructures to greater localization of modes at and around the cutoff frequency of the softer layer as demonstrated via lattice dynamics calculations and diffusivities of individual eigenmodes calculated according to the Allen-Feldman theory [P. B. Allen and J. L. Feldman, Phys. Rev. B 48, 12581 (1993), 10.1103/PhysRevB.48.12581] for our amorphous SiGe-based alloys and superlattice structures.

IEEE Photovoltaic Specialists Conference, 20th, Las Vegas, NV, Sept. 26-30, 1988, Conference Record. Volumes 1 & 2

NASA Astrophysics Data System (ADS)

Various papers on photovoltaics are presented. The general topics considered include: amorphous materials and cells; amorphous silicon-based solar cells and modules; amorphous silicon-based materials and processes; amorphous materials characterization; amorphous silicon; high-efficiency single crystal solar cells; multijunction and heterojunction cells; high-efficiency III-V cells; modeling and characterization of high-efficiency cells; LIPS flight experience; space mission requirements and technology; advanced space solar cell technology; space environmental effects and modeling; space solar cell and array technology; terrestrial systems and array technology; terrestrial utility and stand-alone applications and testing; terrestrial concentrator and storage technology; terrestrial stand-alone systems applications; terrestrial systems test and evaluation; terrestrial flatplate and concentrator technology; use of polycrystalline materials; polycrystalline II-VI compound solar cells; analysis of and fabrication procedures for compound solar cells.

SU-C-207A-05: Feature Based Water Equivalent Path Length (WEPL) Determination for Proton Radiography by the Technique of Time Resolved Dose Measurement

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

Zhang, R; Jee, K; Sharp, G

Purpose: Studies show that WEPL can be determined from modulated dose rate functions (DRF). However, the previous calibration method based on statistics of the DRF is sensitive to energy mixing of protons due to scattering through different materials (termed as range mixing here), causing inaccuracies in the determination of WEPL. This study intends to explore time-domain features of the DRF to reduce the effect of range mixing in proton radiography (pRG) by this technique. Methods: An amorphous silicon flat panel (PaxScan™ 4030CB, Varian Medical Systems, Inc., Palo Alto, CA) was placed behind phantoms to measure DRFs from a proton beammore » modulated by a specially designed modulator wheel. The performance of two methods, the previously used method based on the root mean square (RMS) and the new approach based on time-domain features of the DRF, are compared for retrieving WEPL and RSP from pRG of a Gammex phantom. Results: Calibration by T{sub 80} (the time point for 80% of the major peak) was more robust to range mixing and produced WEPL with improved accuracy. The error of RSP was reduced from 8.2% to 1.7% for lung equivalent material, with the mean error for all other materials reduced from 1.2% to 0.7%. The mean error of the full width at half maximum (FWHM) of retrieved inserts was decreased from 25.85% to 5.89% for the RMS and T{sub 80} method respectively. Monte Carlo simulations in simplified cases also demonstrated that the T{sub 80} method is less sensitive to range mixing than the RMS method. Conclusion: WEPL images have been retrieved based on single flat panel measured DRFs, with inaccuracies reduced by exploiting time-domain features as the calibration parameter. The T{sub 80} method is validated to be less sensitive to range mixing and can thus retrieve the WEPL values in proximity of interfaces with improved numerical and spatial accuracy for proton radiography.« less

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

NASA Astrophysics Data System (ADS)

van Aken, P. A.; Sharp, T. G.; Seifert, F.

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by modelling the amorphization as a decay process. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of stishovite the formation of a transitory structure with Si largely in fivefold coordination is deduced.

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.

Local melting in Al embedded with TiNi powder induced by microarea self-propagating high-temperature synthesis

NASA Astrophysics Data System (ADS)

Yamamoto, Tokujiro

2014-10-01

Microarea self-propagating high-temperature synthesis (microSHS) was ignited by the heat of mixing generated at the boundaries between an Al matrix and TiNi particles during plastic deformation at room temperature. The temperature of the boundaries was rapidly increased by microSHS; the temperature elevation resulted in local melting of the TiNi particle and the surrounding Al matrix, because the heat of mixing was localized in the vicinity of the TiNi particle although the amount of the heat of mixing was limited. Since the amount of the local melting region induced by microSHS is restricted, not only major elements (i.e. Al, Ti and Ni) but also impurities were involved in the solidification followed by local melting. As a result, ?FeNi nanoprecipitates, which have not been reported in SHS studies, were formed by inclusion of Fe, initially included as an impurity in raw materials. The formation mechanism of ?FeNi nanoprecipitates is discussed based on reference to the Al-Fe-Ni ternary alloy phase diagram. It is expected that local melting induced by microSHS is a key phenomonon for amorphization during severe plastic deformation of elemental sheets.

How does spallation microdamage nucleate in bulk amorphous alloys under shock loading?

NASA Astrophysics Data System (ADS)

Huang, X.; Ling, Z.; Zhang, H. S.; Ma, J.; Dai, L. H.

2011-11-01

Specially designed plate-impact experiments have been conducted on a Zr-based amorphous alloy using a single-stage light gas gun. To understand the microdamage nucleation process in the material, the samples are subjected to dynamic tensile loadings of identical amplitude (˜ 3.18 GPa) but with different durations (83-201 ns). A cellular pattern with an equiaxed shape is observed on the spallation surface, which shows that spallation in the tested amorphous alloy is a typical ductile fracture and that microvoids have been nucleated during the process. Based on the observed fracture morphologies of the spallation surface and free-volume theory, we propose a microvoid nucleation model of bulk amorphous alloys. It is found that nucleation of microvoids at the early stage of spallation in amorphous alloys results from diffusion and coalescence of free volume, and that high mean tensile stress plays a dominant role in microvoid nucleation.

Amorphous semiconductor solar cell

DOEpatents

Dalal, Vikram L.

1981-01-01

A solar cell comprising a back electrical contact, amorphous silicon semiconductor base and junction layers and a top electrical contact includes in its manufacture the step of heat treating the physical junction between the base layer and junction layer to diffuse the dopant species at the physical junction into the base layer.

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

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

Composition-dependent structural and transport properties of amorphous transparent conducting oxides

NASA Astrophysics Data System (ADS)

Khanal, Rabi; Buchholz, D. Bruce; Chang, Robert P. H.; Medvedeva, Julia E.

2015-05-01

Structural properties of amorphous In-based oxides, In -X -O with X =Zn , Ga, Sn, or Ge, are investigated using ab initio molecular dynamics liquid-quench simulations. The results reveal that indium retains its average coordination of 5.0 upon 20% X fractional substitution for In, whereas X cations satisfy their natural coordination with oxygen atoms. This finding suggests that the carrier generation is primarily governed by In atoms, in accord with the observed carrier concentration in amorphous In-O and In -X -O . At the same time, the presence of X affects the number of six-coordinated In atoms as well as the oxygen sharing between the InO6 polyhedra. Based on the obtained interconnectivity and spatial distribution of the InO6 and XO x polyhedra in amorphous In -X -O , composition-dependent structural models of the amorphous oxides are derived. The results help explain our Hall mobility measurements in In -X -O thin films grown by pulsed-laser deposition and highlight the importance of long-range structural correlations in the formation of amorphous oxides and their transport properties.

Amorphous Solid Dispersion of Epigallocatechin Gallate for Enhanced Physical Stability and Controlled Release.

PubMed

Cao, Yizheng; Teng, Jing; Selbo, Jon

2017-11-09

Epigallocatechin gallate (EGCG) has been recognized as the most prominent green tea extract due to its healthy influences. The high instability and low bioavailability, however, strongly limit its utilization in food and drug industries. This work, for the first time, develops amorphous solid dispersion of EGCG to enhance its bioavailability and physical stability. Four commonly used polymeric excipients are found to be compatible with EGCG in water-dioxane mixtures via a stepwise mixing method aided by vigorous mechanical interference. The dispersions are successfully generated by lyophilization. The physical stability of the dispersions is significantly improved compared to pure amorphous EGCG in stress condition (elevated temperature and relative humidity) and simulated gastrointestinal tract environment. From the drug release tests, one of the dispersions, EGCG-Soluplus ® 50:50 ( w / w ) shows a dissolution profile that only 50% EGCG is released in the first 20 min, and the remains are slowly released in 24 h. This sustained release profile may open up new possibilities to increase EGCG bioavailability via extending its elimination time in plasma.

Biopreservation of Myoglobin in Crowded Environment: A Comparison between Gelatin and Trehalose Matrixes.

PubMed

Semeraro, Enrico F; Giuffrida, Sergio; Cottone, Grazia; Cupane, Antonio

2017-09-21

Biopreservation by sugar and/or polymeric matrixes is a thoroughly studied research topic with wide technological relevance. Ternary amorphous systems containing both saccharides and proteins are extensively exploited to model the in vivo biopreservation process. With the aim of disentangling the effect of saccharides and polypeptidic crowders (such as gelatin) on the preservation of a model protein, we present here a combined differential scanning calorimetry and UV-vis spectrophotometry study on samples of myoglobin embedded in amorphous gelatin and trehalose + gelatin matrixes at different hydrations, and compare them with amorphous myoglobin-only and myoglobin-trehalose samples. The results point out the different effects of gelatin, which acts mainly as a crowding agent, and trehalose, which acts mainly by direct interaction. Gelatin is able to improve effectively the protein thermal stability at very low hydration; however, it has small effects at medium to high hydration. Consistently, gelatin appears to be more effective than trehalose against massive denaturation in the long time range, while the mixed trehalose + collagen matrix is most effective in preserving protein functionality, outdoing both gelatin-only and trehalose-only matrixes.

Quantitative relations between interaction parameter, miscibility and function in organic solar cells

NASA Astrophysics Data System (ADS)

Ye, Long; Hu, Huawei; Ghasemi, Masoud; Wang, Tonghui; Collins, Brian A.; Kim, Joo-Hyun; Jiang, Kui; Carpenter, Joshua H.; Li, Hong; Li, Zhengke; McAfee, Terry; Zhao, Jingbo; Chen, Xiankai; Lai, Joshua Lin Yuk; Ma, Tingxuan; Bredas, Jean-Luc; Yan, He; Ade, Harald

2018-03-01

Although it is known that molecular interactions govern morphology formation and purity of mixed domains of conjugated polymer donors and small-molecule acceptors, and thus largely control the achievable performance of organic solar cells, quantifying interaction-function relations has remained elusive. Here, we first determine the temperature-dependent effective amorphous-amorphous interaction parameter, χaa(T), by mapping out the phase diagram of a model amorphous polymer:fullerene material system. We then establish a quantitative `constant-kink-saturation' relation between χaa and the fill factor in organic solar cells that is verified in detail in a model system and delineated across numerous high- and low-performing materials systems, including fullerene and non-fullerene acceptors. Our experimental and computational data reveal that a high fill factor is obtained only when χaa is large enough to lead to strong phase separation. Our work outlines a basis for using various miscibility tests and future simulation methods that will significantly reduce or eliminate trial-and-error approaches to material synthesis and device fabrication of functional semiconducting blends and organic blends in general.

Thermoelectric Properties of Nanograined Si-Ge-Au Thin Films Grown by Molecular Beam Deposition

NASA Astrophysics Data System (ADS)

Nishino, Shunsuke; Ekino, Satoshi; Inukai, Manabu; Omprakash, Muthusamy; Adachi, Masahiro; Kiyama, Makoto; Yamamoto, Yoshiyuki; Takeuchi, Tsunehiro

2018-06-01

Conditions to achieve extremely large Seebeck coefficient and extremely small thermal conductivity in Si-Ge-Au thin films formed of nanosized grains precipitated in amorphous matrix have been investigated. We employed molecular beam deposition to prepare Si1- x Ge x Au y thin films on sapphire substrate. The deposited films were annealed under nitrogen gas atmosphere at 300°C to 500°C for 15 min to 30 min. Nanocrystals dispersed in amorphous matrix were clearly observed by transmission electron microscopy. We did not observe anomalously large Seebeck coefficient, but very low thermal conductivity of nearly 1.0 W K-1 m-1 was found at around 0.2 < x < 0.6. The compositional dependence of the thermal conductivity was well accounted for by the compositional dependence of the mixing entropy. Some of these values agree exactly with the amorphous limit predicted by theoretical calculations. The smallest lattice thermal conductivity found for the present samples is lower than that of nanostructured Si-Ge bulk material for which dimensionless figure of merit of ZT ≈ 1 was reported at high temperature.

Amorphous Solid Dispersion of Epigallocatechin Gallate for Enhanced Physical Stability and Controlled Release

PubMed Central

Cao, Yizheng; Teng, Jing; Selbo, Jon

2017-01-01

Epigallocatechin gallate (EGCG) has been recognized as the most prominent green tea extract due to its healthy influences. The high instability and low bioavailability, however, strongly limit its utilization in food and drug industries. This work, for the first time, develops amorphous solid dispersion of EGCG to enhance its bioavailability and physical stability. Four commonly used polymeric excipients are found to be compatible with EGCG in water-dioxane mixtures via a stepwise mixing method aided by vigorous mechanical interference. The dispersions are successfully generated by lyophilization. The physical stability of the dispersions is significantly improved compared to pure amorphous EGCG in stress condition (elevated temperature and relative humidity) and simulated gastrointestinal tract environment. From the drug release tests, one of the dispersions, EGCG-Soluplus® 50:50 (w/w) shows a dissolution profile that only 50% EGCG is released in the first 20 min, and the remains are slowly released in 24 h. This sustained release profile may open up new possibilities to increase EGCG bioavailability via extending its elimination time in plasma. PMID:29120370

Densification behavior, nanocrystallization, and mechanical properties of spark plasma sintered Fe-based bulk amorphous alloys

NASA Astrophysics Data System (ADS)

Singh, Ashish Kumar

Fe-based amorphous alloys are gaining increasing attention due to their exceptional wear and corrosion resistance for potential structural applications. Two major challenges that are hindering the commercialization of these amorphous alloys are difficulty in processing of bulk shapes (diameter > 10 mm) and lack of ductility. Spark plasma sintering (SPS) is evolving as a promising technique for processing bulk shapes of amorphous and nanocrystalline materials. The objective of this work is to investigate densification behavior, nanocrystallization, and mechanical properties of SPS sintered Fe-based amorphous alloys of composition Fe48Cr15Mo14Y2C15B6. SPS processing was performed in three distinct temperature ranges of amorphous alloys: (a) below glass transition temperature (Tg), (b) between Tg and crystallization temperature (Tx), and (c) above Tx. Punch displacement data obtained during SPS sintering was correlated with the SPS processing parameters such as temperature, pressure, and sintering time. Powder rearrangement, plastic deformation below T g, and viscous flow of the material between Tg and Tx were observed as the main densification stages during SPS sintering. Micro-scale temperature distributions at the point of contact and macro-scale temperature distribution throughout the sample during SPS of amorphous alloys were modeled. The bulk amorphous alloys are expected to undergo structural relaxation and nanocrystallization during SPS sintering. X-ray diffraction (XRD), small angle neutron scattering (SANS), and transmission electron microscopy (TEM) was performed to investigate the evolution of nanocrystallites in SPS sintered Fe-based bulk amorphous alloys. The SANS analysis showed significant scattering for the samples sintered in the supercooled region indicating local structural and compositional changes with the profuse nucleation of nano-clusters (~4 nm). Compression tests and microhardness were performed on the samples sintered at different temperatures ranging from 570 °C to 800 °C. Maximum compression strength (1.1+/-0.2 MPa) was obtained for the samples sintered in the supercooled region. Effects of crystallization on tribological behavior of sintered samples were also investigated where crystallization resulted in increase in wear resistance. Laser surface hardening of SPS sintered amorphous samples were performed. Depending on the processing parameters, the laser surface irradiation causes structural relaxation and nanocrystallization, resulting in surface hardening.

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.

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.

Ferromagnetic laser-welded Fe78Si13B9 and Co71.5Fe2.5SigMn2Mo1B14ils amorphous foils

NASA Astrophysics Data System (ADS)

Pawlak, Ryszard

1997-10-01

In the paper the results of attempts at laser welding of amorphous ferromagnetic foils on the iron and cobalt base have been presented. The usefulness of this technology for making small magnetic circuits of metallic glass has been demonstrated. The action of laser radiation leading to rendering the structure amorphous and the infraction of a laser beam with an amorphous material have been discussed. Finally, the results of pulsed welding of a pack of amorphous foils and some properties of the welds formed have been discussed.

Design of Amorphous Manganese Oxide@Multiwalled Carbon Nanotube Fiber for Robust Solid-State Supercapacitor.

PubMed

Shi, Peipei; Li, Li; Hua, Li; Qian, Qianqian; Wang, Pengfei; Zhou, Jinyuan; Sun, Gengzhi; Huang, Wei

2017-01-24

Solid-state fiber-based supercapacitors have been considered promising energy storage devices for wearable electronics due to their lightweight and amenability to be woven into textiles. Efforts have been made to fabricate a high performance fiber electrode by depositing pseudocapacitive materials on the outer surface of carbonaceous fiber, for example, crystalline manganese oxide/multiwalled carbon nanotubes (MnO 2 /MWCNTs). However, a key challenge remaining is to achieve high specific capacitance and energy density without compromising the high rate capability and cycling stability. In addition, amorphous MnO 2 is actually preferred due to its disordered structure and has been proven to exhibit superior electrochemical performance over the crystalline one. Herein, by incorporating amorphous MnO 2 onto a well-aligned MWCNT sheet followed by twisting, we design an amorphous MnO 2 @MWCNT fiber, in which amorphous MnO 2 nanoparticles are distributed in MWCNT fiber uniformly. The proposed structure gives the amorphous MnO 2 @MWCNT fiber good mechanical reliability, high electrical conductivity, and fast ion-diffusion. Solid-state supercapacitor based on amorphous MnO 2 @MWCNT fibers exhibits improved energy density, superior rate capability, exceptional cycling stability, and excellent flexibility. This study provides a strategy to design a high performance fiber electrode with microstructure control for wearable energy storage devices.

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.

Rheology Guided Rational Selection of Processing Temperature To Prepare Copovidone-Nifedipine Amorphous Solid Dispersions via Hot Melt Extrusion (HME).

PubMed

Yang, Fengyuan; Su, Yongchao; Zhang, Jingtao; DiNunzio, James; Leone, Anthony; Huang, Chengbin; Brown, Chad D

2016-10-03

The production of amorphous solid dispersions via hot melt extrusion (HME) relies on elevated temperature and prolonged residence time, which can result in potential degradation and decomposition of thermally sensitive components. Herein, the rheological properties of a physical mixture of polymer and an active pharmaceutical ingredient (API) were utilized to guide the selection of appropriate HME processing temperature. In the currently studied copovidone-nifedipine system, a critical temperature, which is substantially lower (∼13 °C) than the melting point of crystalline API, was captured during a temperature ramp examination and regarded as the critical point at which the API could molecularly dissolve into the polymer. Based on the identification of this critical point, various solid dispersions were prepared by HME processing below, at, and above the critical temperature (both below and above the melting temperature (T m ) of crystalline API). In addition, the resultant extrudates along with two control solid dispersions prepared by physical mixing and cryogenic milling were assessed by X-ray diffraction, differential scanning calorimetry, hot stage microscopy, rheology, and solid-state NMR. Physicochemical properties of resultant solid dispersions indicated that the identified critical temperature is sufficient for the polymer-API system to reach a molecular-level mixing, manifested by the transparent and smooth appearance of extrudates, the absence of API crystalline diffraction and melting peaks, dramatically decreased rheological properties, and significantly improved polymer-API miscibility. Once the critical temperature has been achieved, further raising the processing temperature only results in limited improvement of API dispersion, reflected by slightly reduced storage modulus and complex viscosity and limited improvement in miscibility.

Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol

PubMed Central

2017-01-01

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu–Mg–Al oxide (CuMgAlOx) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO2, Ni2P/SiO2, and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlOx. A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlOx with Ni/SiO2 and especially Ni2P/SiO2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni2P/SiO2, the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products. PMID:28405528

Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol.

PubMed

Korányi, Tamás I; Huang, Xiaoming; Coumans, Alessandro E; Hensen, Emiel J M

2017-04-03

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO 2 , Ni 2 P/SiO 2 , and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO 2 and especially Ni 2 P/SiO 2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni 2 P/SiO 2 , the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.

Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs

NASA Technical Reports Server (NTRS)

Blake, D. F.; Allamandola, L. J.; Sandford, S.; Hudgins, D.; Freund, F.

1991-01-01

In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.

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.

Fabrication of photonic amorphous diamonds for terahertz-wave applications

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

Komiyama, Yuichiro; Abe, Hiroyuki; Kamimura, Yasushi

2016-05-09

A recently proposed photonic bandgap material, named “photonic amorphous diamond” (PAD), was fabricated in a terahertz regime, and its terahertz-wave propagation properties were investigated. The PAD structure was fabricated from acrylic resin mixed with alumina powder, using laser lithographic, micro-additive manufacturing technique. After fabrication, the resulting structure was dewaxed and sintered. The formation of a photonic bandgap at around 0.45 THz was demonstrated by terahertz time-domain spectroscopy. Reflecting the disordered nature of the random network structure, diffusive terahertz-wave propagation was observed in the passbands; the scattering mean-free path decreased as the frequency approached the band edge. The mean-free paths evaluated atmore » the band edges were close to the Ioffe-Regel threshold value for wave localization.« less

Microstructure and physical properties of laser Zn modified amorphous-nanocrystalline coating on a titanium alloy

NASA Astrophysics Data System (ADS)

Li, Jia-Ning; Gong, Shui-Li; Shi, Yi-Ning; Suo, Hong-Bo; Wang, Xi-Chang; Deng, Yun-Hua; Shan, Fei-Hu; Li, Jian-Quan

2014-02-01

A Zn modified amorphous-nanocrystalline coating was fabricated on a Ti-6Al-4V alloy by laser cladding of the Co-Ti-B4C-Zn-Y2O3 mixed powders. Such coating was researched by means of a scanning electron microscope (SEM) and a high resolution transmission electron microscope (HRTEM), etc. Experimental results indicated that the Co5Zn21 and TiB2 nanocrystalline phases were produced through in situ metallurgical reactions, which blocked the motion of dislocation, and TiB2 grew along (010), (111) and (024). The Co5Zn21 nanocrystals were produced attached to the ceramics, which mainly consisted of the Co nanoparticles embedded in a heterogeneous zinc, and had varied crystalline orientations.

Design and Fabrication of a Miniaturized GMI Magnetic Sensor Based on Amorphous Wire by MEMS Technology

PubMed Central

Chen, Jiawen; Li, Jianhua; Li, Yiyuan; Chen, Yulong

2018-01-01

A miniaturized Co-based amorphous wire GMI (Giant magneto-impedance) magnetic sensor was designed and fabricated in this paper. The Co-based amorphous wire was used as the sense element due to its high sensitivity to the magnetic field. A three-dimensional micro coil surrounding the Co-based amorphous wire was fabricated by MEMS (Micro-Electro-Mechanical System) technology, which was used to extract the electrical signal. The three-dimensional micro pick-up coil was designed and simulated with HFSS (High Frequency Structure Simulator) software to determine the key parameters. Surface micro machining MEMS (Micro-Electro-Mechanical System) technology was employed to fabricate the three-dimensional coil. The size of the developed amorphous wire magnetic sensor is 5.6 × 1.5 × 1.1 mm3. Helmholtz coil was used to characterize the performance of the device. The test results of the sensor sample show that the voltage change is 130 mV/Oe and the linearity error is 4.83% in the range of 0~45,000 nT. The results indicate that the developed miniaturized magnetic sensor has high sensitivity. By testing the electrical resistance of the samples, the results also showed high uniformity of each device. PMID:29494477

Encapsulated Vanadium-Based Hybrids in Amorphous N-Doped Carbon Matrix as Anode Materials for Lithium-Ion Batteries.

PubMed

Long, Bei; Balogun, Muhammad-Sadeeq; Luo, Lei; Luo, Yang; Qiu, Weitao; Song, Shuqin; Zhang, Lei; Tong, Yexiang

2017-11-01

Recently, researchers have made significant advancement in employing transition metal compound hybrids as anode material for lithium-ion batteries and developing simple preparation of these hybrids. To this end, this study reports a facile and scalable method for fabricating a vanadium oxide-nitride composite encapsulated in amorphous carbon matrix by simply mixing ammonium metavanadate and melamine as anode materials for lithium-ion batteries. By tuning the annealing temperature of the mixture, different hybrids of vanadium oxide-nitride compounds are synthesized. The electrode material prepared at 700 °C, i.e., VM-700, exhibits excellent cyclic stability retaining 92% of its reversible capacity after 200 cycles at a current density of 0.5 A g -1 and attractive rate performance (220 mAh g -1 ) under the current density of up to 2 A g -1 . The outstanding electrochemical properties can be attributed to the synergistic effect from heterojunction form by the vanadium compound hybrids, the improved ability of the excellent conductive carbon for electron transfer, and restraining the expansion and aggregation of vanadium oxide-nitride in cycling. These interesting findings will provide a reference for the preparation of transition metal oxide and nitride composites as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic molecular structure of plant biomass-derived black carbon (biochar)

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

Keiluweit, M.; Nico, P.S.; Johnson, M.G.

2009-11-15

Char black carbon (BC), the solid residue of incomplete combustion, is continuously being added to soils and sediments due to natural vegetation fires, anthropogenic pollution, and new strategies for carbon sequestration ('biochar'). Here we present a molecular-level assessment of the physical organization and chemical complexity of biomass-derived chars and, specifically, that of aromatic carbon in char structures. BET-N{sub 2} surface area, X-ray diffraction (XRD), synchrotron-based Near-edge X-ray Absorption Fine Structure (NEXAFS), and Fourier transform infrared (FT-IR) spectroscopy are used to show how two plant materials (wood and grass) undergo analogous, but quantitatively different physical-chemical transitions as charring temperature increases frommore » 100 to 700 C. These changes suggest the existence of four distinct categories of char consisting of a unique mixture of chemical phases and physical states: (i) in transition chars the crystalline character of the precursor materials is preserved, (ii) in amorphous chars the heat-altered molecules and incipient aromatic polycondensates are randomly mixed, (iii) composite chars consist of poorly ordered graphene stacks embedded in amorphous phases, and (iv) turbostratic chars are dominated by disordered graphitic crystallites. The molecular variations among the different char categories translate into differences in their ability to persist in the environment and function as environmental sorbents.« less

Wavelength-agile near-IR optical parametric oscillator using a deposited silicon waveguide.

PubMed

Wang, Ke-Yao; Foster, Mark A; Foster, Amy C

2015-06-15

Using a deposited hydrogenated amorphous silicon (a-Si:H) waveguide, we demonstrate ultra-broad bandwidth (60 THz) parametric amplification via four-wave mixing (FWM), and subsequently achieve the first silicon optical parametric oscillator (OPO) at near-IR wavelengths. Utilization of the time-dispersion-tuned technique provides an optical source with active wavelength tuning over 42 THz with a fixed pump wave.

The Role of Siliceous Hydrothermal Breccias in the Genesis of Volcanic Massive Sulphide Deposits - Ancient and Recent Systems

NASA Astrophysics Data System (ADS)

Costa, I. A.; Barriga, F. J.; Fouquet, Y.

2014-12-01

Siliceous hydrothermal breccias were sampled in two Mid-Atlantic Ridge active sites: Lucky Strike and Menez Gwen. These hydrothermal fields are located in the border of the Azorean plateau, southwest of the Azores islands where the alteration processes affecting basaltic rocks are prominent (Costa et al., 2003). The hydrothermal breccias are genetically related with the circulation of low temperature hydrothermal fluids in diffuse vents. The groundmass of these breccias precipitates from the fluid and consolidates the clastic fragments mostly composed of basalt. The main sources are the surrounding volcanic hills. Breccias are found near hydrothermal vents and may play an important role in the protection of subseafloor hydrothermal deposits forming an impermeable cap due to the high content in siliceous material. The amorphous silica tends to precipitate when the fluid is conductively cooled as proposed by Fouquet et al. (1998) after Fournier (1983). The process evolves gradually from an initial stage where we have just the fragments and circulating seawater. The ascending hydrothermal fluid mixes with seawater, which favours the precipitation of the sulphide components. Sealing of the initially loose fragments begins, the temperature rises below this crust, and the processes of mixing fluid circulation and conductive cooling are simultaneous. At this stage the fluid becomes oversaturated with respect to amorphous silica. This form of silica can precipitate in the open spaces of the porous sulphides and seal the system. Normally this can happen at low temperatures. At this stage the hydrothermal breccia is formed creating a progressively less permeable, eventually impermeable cap rock at the surface. Once the fluid is trapped under this impermeable layer, conductive cooling is enhanced and mixing with seawater is restricted, making the precipitation of amorphous silica more efficient. Since the first discovery and description of recent mineralized submarine hydrothermal deposits, comparison with ancient volcanic massive sulphide deposits is appropriate. The proposed model can explain some of the processes taking place in the early phase of formation of old deposits where equivalent siliceous material is found in the hanging wall of the ore bodies (e.g. Barriga and Fyfe, 1988).

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.

Structure and Properties of SiO x Films Prepared by Chemical Etching of Amorphous Alloy Ribbons

NASA Astrophysics Data System (ADS)

Fedorov, V. A.; Berezner, A. D.; Beskrovnyi, A. I.; Fursova, T. N.; Pavlikov, A. V.; Bazhenov, A. V.

2018-04-01

The structure and the physical properties of amorphous SiO x films prepared by chemical etching of an iron-based amorphous ribbon alloy have been studied. The neutron diffraction and also the atomicforce and electron microscopy show that the prepared visually transparent films have amorphous structure, exhibit dielectric properties, and their morphology is similar to that of opals. The samples have been studied by differential scanning calorimetry, Raman and IR spectroscopy before and after their heat treatment. It is found that annealing of the films in air at a temperature of 1273 K leads to a change in their chemical compositions: an amorphous SiO2 compound with inclusions of SiO2 nanocrystals (crystobalite) forms.

Molecular Dynamical Simulation of Thermal Conductivity in Amorphous Structures

NASA Astrophysics Data System (ADS)

Deangelis, Freddy; Henry, Asegun

While current descriptions of thermal transport exists for well-ordered materials such as crystal latices, new methods are needed to describe thermal transport in disordered materials, including amorphous solids. Because such structures lack periodic, long-range order, a group velocity cannot be defined for thermal modes of vibration; thus, the phonon gas model cannot be applied to these structures. Instead, a new framework must be applied to analyze such materials. Using a combination of density functional theory and molecular dynamics, we have analyzed thermal transport in amorphous structures, chiefly amorphous germanium. The analysis allows us to categorize vibrational modes as propagons, diffusons, or locons, and to determine how they contribute to thermal conductivity within amorphous structures. This method is also being extended to other disordered structures such as amorphous polymers. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1148903.

Amorphization of nanocrystalline 3C-SiC irradiated with Si+ ions

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

Jiang, Weilin; Wang, Haiyan; Kim, Ickchan

2010-11-23

Irradiation induced amorphization in nanocrystalline and single crystal 3C-SiC has been studied using 1 MeV Si+ ions under the identical irradiation conditions at room temperature and 400 K. The disordering behavior has been characterized using in-situ ion channeling and ex-situ x-ray diffraction methods. The results show that, compared to single crystal 3C-SiC, full amorphization of small 3C-SiC grains (~3.8 nm in size) occurs at a slightly lower dose at room temperature. For grains with sizes of 3.0 - 3.8 nm, the amorphization dose is lower at room temperature than 400 K. A significantly lower dose for amorphization of smaller grainsmore » (2.0 nm in size) is observed at 400 K. The behavior has been interpreted based on the competition between the interface and interior amorphization.« 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.

Molecular dynamics simulations of hydrogen bombardment of tungsten carbide surfaces

NASA Astrophysics Data System (ADS)

Träskelin, P.; Juslin, N.; Erhart, P.; Nordlund, K.

2007-05-01

The interaction between energetic hydrogen and tungsten carbide (WC) is of interest both due to the use of hydrogen-containing plasmas in thin-film manufacturing and due to the presence of WC in the divertor of fusion reactors. In order to study this interaction, we have carried out molecular dynamics simulations of the low-energy bombardment of deuterium impinging onto crystalline as well as amorphous WC surfaces. We find that prolonged bombardment leads to the formation of an amorphous WC surface layer, regardless of the initial structure of the WC sample. Loosely bound hydrocarbons, which can erode by swift chemical sputtering, are formed at the surface. Carbon-terminated surfaces show larger sputtering yields than tungsten-terminated surfaces. In both cumulative and noncumulative simulations, C is seen to sputter preferentially. Implications for mixed material erosion in ITER are discussed.

Rubidium as an Alternative Cation for Efficient Perovskite Light-Emitting Diodes.

PubMed

Kanwat, Anil; Moyen, Eric; Cho, Sinyoung; Jang, Jin

2018-05-16

Incorporation of rubidium (Rb) into mixed lead halide perovskites has recently achieved record power conversion efficiency and excellent stability in perovskite solar cells. Inspired by these tremendous advances in photovoltaics, this study demonstrates the impact of Rb incorporation into MAPbBr 3 -based light emitters. Rb partially substitutes MA (methyl ammonium), resulting in a mixed cation perovskite with the formula MA (1- x) Rb x PbBr 3 . Pure MAPbBr 3 crystallizes into a polycrystalline layer with highly defective sub-micrometer grains. However, the addition of a small amount of Rb forms MA (1- x) Rb x PbBr 3 nanocrystals (10 nm) embedded in an amorphous matrix of MA/Rb Br. These nanocrystals grow into defect-free sub-micrometer-sized crystallites with further addition of Rb, resulting in a 3-fold increase in exciton lifetime when the molar ratio of MABr/RbBr is 1:1. A thin film fabricated with a 1:1 molar ratio of MABr/RbBr showed the best electroluminescent properties with a current efficiency (CE) of 9.45 cd/A and a luminance of 7694 cd/m 2 . These values of CE and luminance are, respectively, 19 and 10 times larger than those achieved by pure MAPbBr 3 devices (0.5 cd/A and 790 cd/m 2 ). We believe this work provides important information on the future compositional optimization of Rb + -based mixed cation perovskites for obtaining high-performance light-emitting diodes.

Ion-Beam-Induced Atomic Mixing in Ge, Si, and SiGe, Studied by Means of Isotope Multilayer Structures

PubMed Central

Radek, Manuel; Liedke, Bartosz; Schmidt, Bernd; Voelskow, Matthias; Bischoff, Lothar; Lundsgaard Hansen, John; Nylandsted Larsen, Arne; Bougeard, Dominique; Böttger, Roman; Prucnal, Slawomir; Posselt, Matthias; Bracht, Hartmut

2017-01-01

Crystalline and preamorphized isotope multilayers are utilized to investigate the dependence of ion beam mixing in silicon (Si), germanium (Ge), and silicon germanium (SiGe) on the atomic structure of the sample, temperature, ion flux, and electrical doping by the implanted ions. The magnitude of mixing is determined by secondary ion mass spectrometry. Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy, and transmission electron microscopy provide information about the structural state after ion irradiation. Different temperature regimes with characteristic mixing properties are identified. A disparity in atomic mixing of Si and Ge becomes evident while SiGe shows an intermediate behavior. Overall, atomic mixing increases with temperature, and it is stronger in the amorphous than in the crystalline state. Ion-beam-induced mixing in Ge shows no dependence on doping by the implanted ions. In contrast, a doping effect is found in Si at higher temperature. Molecular dynamics simulations clearly show that ion beam mixing in Ge is mainly determined by the thermal spike mechanism. In the case of Si thermal spike, mixing prevails at low temperature whereas ion beam-induced enhanced self-diffusion dominates the atomic mixing at high temperature. The latter process is attributed to highly mobile Si di-interstitials formed under irradiation and during damage annealing. PMID:28773172

Ion-Beam-Induced Atomic Mixing in Ge, Si, and SiGe, Studied by Means of Isotope Multilayer Structures.

PubMed

Radek, Manuel; Liedke, Bartosz; Schmidt, Bernd; Voelskow, Matthias; Bischoff, Lothar; Hansen, John Lundsgaard; Larsen, Arne Nylandsted; Bougeard, Dominique; Böttger, Roman; Prucnal, Slawomir; Posselt, Matthias; Bracht, Hartmut

2017-07-17

Crystalline and preamorphized isotope multilayers are utilized to investigate the dependence of ion beam mixing in silicon (Si), germanium (Ge), and silicon germanium (SiGe) on the atomic structure of the sample, temperature, ion flux, and electrical doping by the implanted ions. The magnitude of mixing is determined by secondary ion mass spectrometry. Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy, and transmission electron microscopy provide information about the structural state after ion irradiation. Different temperature regimes with characteristic mixing properties are identified. A disparity in atomic mixing of Si and Ge becomes evident while SiGe shows an intermediate behavior. Overall, atomic mixing increases with temperature, and it is stronger in the amorphous than in the crystalline state. Ion-beam-induced mixing in Ge shows no dependence on doping by the implanted ions. In contrast, a doping effect is found in Si at higher temperature. Molecular dynamics simulations clearly show that ion beam mixing in Ge is mainly determined by the thermal spike mechanism. In the case of Si thermal spike, mixing prevails at low temperature whereas ion beam-induced enhanced self-diffusion dominates the atomic mixing at high temperature. The latter process is attributed to highly mobile Si di-interstitials formed under irradiation and during damage annealing.

Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

PubMed

Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

2014-02-28

The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

Transmission electron microscopy of coatings formed by plasma electrolytic oxidation of titanium.

PubMed

Matykina, E; Arrabal, R; Skeldon, P; Thompson, G E

2009-05-01

Transmission electron microscopy and supporting film analyses are used to investigate the changes in composition, morphology and structure of coatings formed on titanium during DC plasma electrolytic oxidation in a calcium- and phosphorus-containing electrolyte. The coatings are of potential interest as bioactive surfaces. The initial barrier film, of mixed amorphous and nanocrystalline structure, formed below the sparking voltage of 180 V, incorporates small amounts of phosphorus and calcium species, with phosphorus confined to the outer approximately 63% of the coating thickness. On commencement of sparking, calcium- and phosphorus-rich amorphous material forms at the coating surface, with local heating promoting crystallization in underlying and adjacent anodic titania. The amorphous material thickens with increased treatment time, comprising almost the whole of the approximately 5.7-microm-thick coating formed at 340 V. At this stage, the coating is approximately 4.4 times thicker than the oxidized titanium, with a near-surface composition of about 12 at.% Ti, 58 at.% O, 19 at.% P and 11 at.% Ca. Further, the amount of titanium consumed in forming the coating is similar to that calculated from the anodizing charge, although there may be non-Faradaic contributions to the coating growth.

Fe-Based Amorphous Coatings on AISI 4130 Structural Steel for Corrosion Resistance

NASA Astrophysics Data System (ADS)

Katakam, Shravana; Santhanakrishnan, S.; Dahotre, Narendra B.

2012-06-01

The current study focuses on synthesizing a novel functional coating for corrosion resistance applications, via laser surface alloying. The iron-based (Fe48Cr15Mo14Y2C15B) amorphous precursor powder is used for laser surface alloying on AISI 4130 steel substrate, with a continuous wave ytterbium Nd-YAG fiber laser. The corrosion resistance of the coatings is evaluated for different processing conditions. The microstructural evolution and the response of the microstructure to the corrosive environment is studied using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Microstructural studies indicate the presence of face-centered cubic Fe-based dendrites intermixed within an amorphous matrix along with fine crystalline precipitates. The corrosion resistance of the coatings decrease with an increase in laser energy density, which is attributed to the precipitation and growth of chromium carbide. The enhanced corrosion resistance of the coatings processed with low energy density is attributed to the self-healing mechanism of this amorphous system.

COHESION OF AMORPHOUS SILICA SPHERES: TOWARD A BETTER UNDERSTANDING OF THE COAGULATION GROWTH OF SILICATE DUST AGGREGATES

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

Kimura, Hiroshi; Wada, Koji; Senshu, Hiroki

2015-10-10

Adhesion forces between submicrometer-sized silicate grains play a crucial role in the formation of silicate dust agglomerates, rocky planetesimals, and terrestrial planets. The surface energy of silicate dust particles is the key to their adhesion and rolling forces in a theoretical model based on contact mechanics. Here we revisit the cohesion of amorphous silica spheres by compiling available data on the surface energy for hydrophilic amorphous silica in various circumstances. It turned out that the surface energy for hydrophilic amorphous silica in a vacuum is a factor of 10 higher than previously assumed. Therefore, the previous theoretical models underestimated themore » critical velocity for the sticking of amorphous silica spheres, as well as the rolling friction forces between them. With the most plausible value of the surface energy for amorphous silica spheres, theoretical models based on the contact mechanics are in harmony with laboratory experiments. Consequently, we conclude that silicate grains with a radius of 0.1 μm could grow to planetesimals via coagulation in a protoplanetary disk. We argue that the coagulation growth of silicate grains in a molecular cloud is advanced either by organic mantles rather than icy mantles or, if there are no mantles, by nanometer-sized grain radius.« less

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.

Ultrasensitive Surface-Enhanced Raman Spectroscopy Detection Based on Amorphous Molybdenum Oxide Quantum Dots.

PubMed

Li, Hao; Xu, Qun; Wang, Xuzhe; Liu, Wei

2018-06-07

Surface-enhanced Raman spectroscopy (SERS) based on plasmonic semiconductive material has been proved to be an efficient tool to detect trace of substances, while the relatively weak plasmon resonance compared with noble metal materials restricts its practical application. Herein, for the first time a facile method to fabricate amorphous H x MoO 3 quantum dots with tunable plasmon resonance is developed by a controlled oxidization route. The as-prepared amorphous H x MoO 3 quantum dots show tunable plasmon resonance in the region of visible and near-infrared light. Moreover, the tunability induced by SC CO 2 is analyzed by a molecule kinetic theory combined with a molecular thermodynamic model. More importantly, the ultrahigh enhancement factor of amorphous H x MoO 3 quantum dots detecting on methyl blue can be up to 9.5 × 10 5 with expending the limit of detection to 10 -9 m. Such a remarkable porperty can also be found in this H x MoO 3 -based sensor with Rh6G and RhB as probe molecules, suggesting that the amorphous H x MoO 3 quantum dot is an efficient candidate for SERS on molecule detection in high precision. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ observation of stishovite formation in shock-compressed fused silica

NASA Astrophysics Data System (ADS)

Tracy, Sally June; Turneaure, Stefan; Duffy, Thomas

2017-06-01

Silica, SiO2, has widespread applications ranging from optical components to refractory materials and is of geological importance as one of the major oxide components of the Earth's crust and mantle. The response of silica phases to dynamic loading has long been of interest for understanding the structural evolution of this fundamental oxide. Under shock compression both crystalline quartz and fused silica are characterized by the occurrence of a broad `mixed-phase region' (15-40 GPa) and a dense, high-pressure phase with much lower compressibility. Despite decades of study, the nature of this transformation and the identity of the high-pressure phase(s) remain poorly understood. In situ x-ray diffraction experiments on shock-compressed fused silica were conducted at the Dynamic Compression Sector of the Advanced Photon Source. The lattice-level structure was investigated through time-resolved x-ray diffraction measurements on samples reaching peak stress ranging from 12 to 47 GPa. Our results demonstrate that SiO2 adopts a dense amorphous structure in the `mixed-phase region' and abruptly transforms to stishovite above 34 GPa. These results provide clear evidence that high-pressure crystalline silicate phases can form from amorphous starting materials on the time-scale of laboratory shock experiments.

Hydrolysis of the amorphous cellulose in cotton-based paper.

PubMed

Stephens, Catherine H; Whitmore, Paul M; Morris, Hannah R; Bier, Mark E

2008-04-01

Hydrolysis of cellulose in Whatman no. 42 cotton-based paper was studied using gel permeation chromatography (GPC), electrospray ionization-mass spectrometry (ESI-MS), and uniaxial tensile testing to understand the course and kinetics of the reaction. GPC results suggested that scission reactions passed through three stages. Additionally, the evolution of soluble oligomers in the ESI-MS data and the steady course of strength loss showed that the hydrolysis reaction occurred at a constant rate. These findings are explained with a more detailed description of the cellulose hydrolysis, which includes multiple chain scissions on amorphous segments. The breaks occur with increasing frequency near the ends of amorphous segments, where chains protrude from crystalline domains. Oligomers unattached to crystalline domains are eventually created. Late-stage reactions near the ends of amorphous segments produce a kinetic behavior that falsely suggests that hydrolysis had ceased. Monte Carlo simulations of cellulose degradation corroborated the experimental findings.

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.

Enhanced thermoelectric performance of amorphous Nb based oxynitrides

NASA Astrophysics Data System (ADS)

Music, Denis; Geyer, Richard W.; Hans, Marcus

2015-12-01

Using density functional theory, amorphous Nb0.27Ru0.06O0.56N0.10 was designed to facilitate a combination of an enhanced Seebeck coefficient and low electrical resistivity. Based on a positive Cauchy pressure, ductile behavior is expected. To verify these predictions, the transport and mechanical properties of amorphous thin films were evaluated. Metallic electrical resistivity and the Seebeck coefficient of -94 μV K-1 are obtained, which is consistent with our predictions. As there is no crack formation, these samples can be perceived as ductile. We demonstrate that the power factor can be increased by an order of magnitude, while keeping the thermal fatigue low.

Effect of chromium and phosphorus on the physical properties of iron and titanium-based amorphous metallic alloy films

NASA Technical Reports Server (NTRS)

Distefano, S.; Rameshan, R.; Fitzgerald, D. J.

1991-01-01

Amorphous iron and titanium-based alloys containing various amounts of chromium, phosphorus, and boron exhibit high corrosion resistance. Some physical properties of Fe and Ti-based metallic alloy films deposited on a glass substrate by a dc-magnetron sputtering technique are reported. The films were characterized using differential scanning calorimetry, stress analysis, SEM, XRD, SIMS, electron microprobe, and potentiodynamic polarization techniques.

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.

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.

Using machine learning to identify factors that govern amorphization of irradiated pyrochlores

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

Pilania, Ghanshyam; Whittle, Karl R.; Jiang, Chao

Structure–property relationships are a key materials science concept that enables the design of new materials. In the case of materials for application in radiation environments, correlating radiation tolerance with fundamental structural features of a material enables materials discovery. Here, we use a machine learning model to examine the factors that govern amorphization resistance in the complex oxide pyrochlore (A 2B 2O 7) in a regime in which amorphization occurs as a consequence of defect accumulation. We examine the fidelity of predictions based on cation radii and electronegativities, the oxygen positional parameter, and the energetics of disordering and amorphizing the material.more » No one factor alone adequately predicts amorphization resistance. We find that when multiple families of pyrochlores (with different B cations) are considered, radii and electronegativities provide the best prediction, but when the machine learning model is restricted to only the B = Ti pyrochlores, the energetics of disordering and amorphization are critical factors. We discuss how these static quantities provide insight into an inherently kinetic property such as amorphization resistance at finite temperature. Lastly, this work provides new insight into the factors that govern the amorphization susceptibility and highlights the ability of machine learning approaches to generate that insight.« less

Using machine learning to identify factors that govern amorphization of irradiated pyrochlores

DOE PAGES

Pilania, Ghanshyam; Whittle, Karl R.; Jiang, Chao; ...

2017-02-10

Structure–property relationships are a key materials science concept that enables the design of new materials. In the case of materials for application in radiation environments, correlating radiation tolerance with fundamental structural features of a material enables materials discovery. Here, we use a machine learning model to examine the factors that govern amorphization resistance in the complex oxide pyrochlore (A 2B 2O 7) in a regime in which amorphization occurs as a consequence of defect accumulation. We examine the fidelity of predictions based on cation radii and electronegativities, the oxygen positional parameter, and the energetics of disordering and amorphizing the material.more » No one factor alone adequately predicts amorphization resistance. We find that when multiple families of pyrochlores (with different B cations) are considered, radii and electronegativities provide the best prediction, but when the machine learning model is restricted to only the B = Ti pyrochlores, the energetics of disordering and amorphization are critical factors. We discuss how these static quantities provide insight into an inherently kinetic property such as amorphization resistance at finite temperature. Lastly, this work provides new insight into the factors that govern the amorphization susceptibility and highlights the ability of machine learning approaches to generate that insight.« less

Mixed-mode crack tip loading and crack deflection in 1D quasicrystals

NASA Astrophysics Data System (ADS)

Wang, Zhibin; Scheel, Johannes; Ricoeur, Andreas

2016-12-01

Quasicrystals (QC) are a new class of materials besides crystals and amorphous solids and have aroused much attention of researchers since they were discovered. This paper presents a generalized fracture theory including the J-integral and crack closure integrals, relations between J1, J2 and the stress intensity factors as well as the implementation of the near-tip stress and displacement solutions of 1D QC. Different crack deflection criteria, i.e. the J-integral and maximum circumferential stress criteria, are investigated for mixed-mode loading conditions accounting for phonon-phason coupling. One focus is on the influence of phason stress intensity factors on crack deflection angles.

HRTEM low dose: the unfold of the morphed graphene, from amorphous carbon to morphed graphenes.

PubMed

Calderon, H A; Okonkwo, A; Estrada-Guel, I; Hadjiev, V G; Alvarez-Ramírez, F; Robles Hernández, F C

We present experimental evidence under low-dose conditions transmission electron microscopy for the unfolding of the evolving changes in carbon soot during mechanical milling. The milled soot shows evolving changes as a function of the milling severity or time. Those changes are responsible for the transformation from amorphous carbon to graphenes, graphitic carbon, and highly ordered structures such as morphed graphenes, namely Rh6 and Rh6-II. The morphed graphenes are corrugated layers of carbon with cross-linked covalently nature and sp 2 - or sp 3 -type allotropes. Electron microscopy and numerical simulations are excellent complementary tools to identify those phases. Furthermore, the TEAM 05 microscope is an outstanding tool to resolve the microstructure and prevent any damage to the sample. Other characterization techniques such as XRD, Raman, and XPS fade to convey a true identification of those phases because the samples are usually blends or mixes of the mentioned phases.

Simultaneous Pressure-Induced Magnetic and Valence Transitions in Type-I Clathrate Eu8Ga16Ge30

NASA Astrophysics Data System (ADS)

Onimaru, Takahiro; Tsutsui, Satoshi; Mizumaki, Masaichiro; Kawamura, Naomi; Ishimatsu, Naoki; Avila, Marcos A.; Yamamoto, Shuhei; Yamane, Haruki; Suekuni, Koichiro; Umeo, Kazunori; Kume, Tetsuji; Nakano, Satoshi; Takabatake, Toshiro

2014-01-01

We have performed X-ray magnetic circular dichroism (XMCD) and X-ray absorption spectroscopy (XAS) measurements at pressures up to 17 GPa for the clathrate Eu8Ga16Ge30 (Curie temperature TC = 36 K). The temperature dependence of the XMCD spectra agrees well with that of the DC magnetization at ambient pressure. The TC is gradually enhanced with increasing pressures up to 13.3 GPa, and the divalent state of the Eu ions with J = 7/2 remains stable, but at 17 GPa the XMCD intensity is strongly suppressed and a spectral weight corresponding to the trivalent state of Eu ions (with no magnetic moment) appears in the XAS spectrum. The concurrent change from the type-I clathrate structure to an amorphous phase has been observed by X-ray diffraction experiment. We conclude that the amorphization of this compound induces the mixed valence state, which collapses the ferromagnetism.

Crystal nucleation initiated by transient ion-surface interactions at aerosol interfaces

PubMed Central

Davis, Ryan D.; Tolbert, Margaret A.

2017-01-01

Particle collisions are a common occurrence in the atmosphere, but no empirical observations exist to fully predict the potential effects of these collisions on air quality and climate projections. The current consensus of heterogeneous crystal nucleation pathways relevant to the atmosphere dictates that collisions with amorphous particles have no effect on the crystallization relative humidity (RH) of aqueous inorganic aerosols because there is no stabilizing ion-surface interaction to facilitate the formation of crystal nuclei. In contrast to this view of heterogeneous nucleation, we report laboratory observations demonstrating that collisions with hydrophobic amorphous organic aerosols induced crystallization of aqueous inorganic microdroplets at high RH, the effect of which was correlated with destabilizing water-mediated ion-specific surface interactions. These same organic aerosols did not induce crystallization once internally mixed in the droplet, pointing toward a previously unconsidered transient ion-specific crystal nucleation pathway that can promote aerosol crystallization via particle collisions. PMID:28776032

Crystal nucleation initiated by transient ion-surface interactions at aerosol interfaces.

PubMed

Davis, Ryan D; Tolbert, Margaret A

2017-07-01

Particle collisions are a common occurrence in the atmosphere, but no empirical observations exist to fully predict the potential effects of these collisions on air quality and climate projections. The current consensus of heterogeneous crystal nucleation pathways relevant to the atmosphere dictates that collisions with amorphous particles have no effect on the crystallization relative humidity (RH) of aqueous inorganic aerosols because there is no stabilizing ion-surface interaction to facilitate the formation of crystal nuclei. In contrast to this view of heterogeneous nucleation, we report laboratory observations demonstrating that collisions with hydrophobic amorphous organic aerosols induced crystallization of aqueous inorganic microdroplets at high RH, the effect of which was correlated with destabilizing water-mediated ion-specific surface interactions. These same organic aerosols did not induce crystallization once internally mixed in the droplet, pointing toward a previously unconsidered transient ion-specific crystal nucleation pathway that can promote aerosol crystallization via particle collisions.

Nanoscale decomposition of Nb-Ru-O

NASA Astrophysics Data System (ADS)

Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

2016-11-01

A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

Energy release properties of amorphous boron and boron-based propellant primary combustion products

NASA Astrophysics Data System (ADS)

Liang, Daolun; Liu, Jianzhong; Xiao, Jinwu; Xi, Jianfei; Wang, Yang; Zhang, Yanwei; Zhou, Junhu

2015-07-01

The microstructure of amorphous boron and the primary combustion products of boron-based fuel-rich propellant (hereafter referred to as primary combustion products) was analyzed by scanning electron microscope. Composition analysis of the primary combustion products was carried out by X-ray diffraction and X-ray photoelectron spectroscopy. The energy release properties of amorphous boron and the primary combustion products were comparatively studied by laser ignition experimental system and thermogravimetry-differential scanning calorimetry. The primary combustion products contain B, C, Mg, Al, B4C, B13C2, BN, B2O3, NH4Cl, H2O, and so on. The energy release properties of primary combustion products are different from amorphous boron, significantly. The full-time spectral intensity of primary combustion products at a wavelength of 580 nm is ~2% lower than that of amorphous boron. The maximum spectral intensity of the former at full wave is ~5% higher than that of the latter. The ignition delay time of primary combustion products is ~150 ms shorter than that of amorphous boron, and the self-sustaining combustion time of the former is ~200 ms longer than that of the latter. The thermal oxidation process of amorphous boron involves water evaporation (weight loss) and boron oxidation (weight gain). The thermal oxidation process of primary combustion products involves two additional steps: NH4Cl decomposition (weight loss) and carbon oxidation (weight loss). CL-20 shows better combustion-supporting effect than KClO4 in both the laser ignition experiments and the thermal oxidation experiments.

Modeling Physical Stability of Amorphous Solids Based on Temperature and Moisture Stresses.

PubMed

Zhu, Donghua Alan; Zografi, George; Gao, Ping; Gong, Yuchuan; Zhang, Geoff G Z

2016-09-01

Isothermal microcalorimetry was utilized to monitor the crystallization process of amorphous ritonavir (RTV) and its hydroxypropylmethylcellulose acetate succinate-based amorphous solid dispersion under various stressed conditions. An empirical model was developed: ln(τ)=ln(A)+EaRT-b⋅wc, where τ is the crystallization induction period, A is a pre-exponential factor, Ea is the apparent activation energy, b is the moisture sensitivity parameter, and wc is water content. To minimize the propagation of errors associated with the estimates, a nonlinear approach was used to calculate mean estimates and confidence intervals. The physical stability of neat amorphous RTV and RTV in hydroxypropylmethylcellulose acetate succinate solid dispersions was found to be mainly governed by the nucleation kinetic process. The impact of polymers and moisture on the crystallization process can be quantitatively described by Ea and b in this Arrhenius-type model. The good agreement between the measured values under some less stressful test conditions and those predicted, reflected by the slope and R(2) of the correlation plot of these 2 sets of data on a natural logarithm scale, indicates its predictability of long-term physical stability of amorphous RTV in solid dispersions. To further improve the model, more understanding of the impact of temperature and moisture on the amorphous physical stability and fundamentals regarding nucleation and crystallization is needed. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

High Purity and Yield of Boron Nitride Nanotubes Using Amorphous Boron and a Nozzle-Type Reactor

PubMed Central

Kim, Jaewoo; Seo, Duckbong; Yoo, Jeseung; Jeong, Wanseop; Seo, Young-Soo; Kim, Jaeyong

2014-01-01

Enhancement of the production yield of boron nitride nanotubes (BNNTs) with high purity was achieved using an amorphous boron-based precursor and a nozzle-type reactor. Use of a mixture of amorphous boron and Fe decreases the milling time for the preparation of the precursor for BNNTs synthesis, as well as the Fe impurity contained in the B/Fe interdiffused precursor nanoparticles by using a simple purification process. We also explored a nozzle-type reactor that increased the production yield of BNNTs compared to a conventional flow-through reactor. By using a nozzle-type reactor with amorphous boron-based precursor, the weight of the BNNTs sample after annealing was increased as much as 2.5-times with much less impurities compared to the case for the flow-through reactor with the crystalline boron-based precursor. Under the same experimental conditions, the yield and quantity of BNNTs were estimated as much as ~70% and ~1.15 g/batch for the former, while they are ~54% and 0.78 g/batch for the latter. PMID:28788161

High Purity and Yield of Boron Nitride Nanotubes Using Amorphous Boron and a Nozzle-Type Reactor.

PubMed

Kim, Jaewoo; Seo, Duckbong; Yoo, Jeseung; Jeong, Wanseop; Seo, Young-Soo; Kim, Jaeyong

2014-08-11

Enhancement of the production yield of boron nitride nanotubes (BNNTs) with high purity was achieved using an amorphous boron-based precursor and a nozzle-type reactor. Use of a mixture of amorphous boron and Fe decreases the milling time for the preparation of the precursor for BNNTs synthesis, as well as the Fe impurity contained in the B/Fe interdiffused precursor nanoparticles by using a simple purification process. We also explored a nozzle-type reactor that increased the production yield of BNNTs compared to a conventional flow-through reactor. By using a nozzle-type reactor with amorphous boron-based precursor, the weight of the BNNTs sample after annealing was increased as much as 2.5-times with much less impurities compared to the case for the flow-through reactor with the crystalline boron-based precursor. Under the same experimental conditions, the yield and quantity of BNNTs were estimated as much as ~70% and ~1.15 g/batch for the former, while they are ~54% and 0.78 g/batch for the latter.

Cu3(BTC)2: CO oxidation over MOF based catalysts.

PubMed

Ye, Jing-yun; Liu, Chang-jun

2011-02-21

Crystalline and amorphized MOFs (Cu(3)(BTC)(2)) have been demonstrated to be excellent catalysts for CO oxidation. The catalytic activity can be further improved by loading PdO(2) nanoparticles onto the amorphized Cu(3)(BTC)(2).

Silicon/Carbon Anodes with One-Dimensional Pore Structure for Lithium-Ion Batteries

DTIC Science & Technology

2013-08-31

Connected by Single-Wall Carbon Nanotubes for Sodium Ion Battery Cathodes, Nano Letters 12, 5664, 2012. ( § equal contribution)  Chao Luo,§ Yunhua...is superior to that of those conductive additive-incorporated iron oxide anodes, such as amorphous carbon , graphene as well as carbon nanotubes ...electrochemical performance. The C/S composite cathodes were prepared by mixing C/S powders with carbon black and sodium carboxymethyl cellulose (CMC

Anti-biofouling function of amorphous nano-Ta2O5 coating for VO2-based intelligent windows.

PubMed

Li, Jinhua; Guo, Geyong; Wang, Jiaxing; Zhou, Huaijuan; Shen, Hao; Yeung, Kelvin W K

2017-04-28

From environmental and health perspectives, the acquisition of a surface anti-biofouling property holds important significance for the usability of VO 2 intelligent windows. Herein, we firstly deposited amorphous Ta 2 O 5 nanoparticles on VO 2 film by the magnetron sputtering method. It was found that the amorphous nano-Ta 2 O 5 coating possessed a favorable anti-biofouling capability against Pseudomonas aeruginosa as an environmental microorganism model, behind which lay the mechanism that the amorphous nano-Ta 2 O 5 could interrupt the microbial membrane electron transport chain and significantly elevate the intracellular reactive oxygen species (ROS) level. A plausible relationship was established between the anti-biofouling activity and physicochemical nature of amorphous Ta 2 O 5 nanoparticles from the perspective of defect chemistry. ROS-induced oxidative damage gave rise to microbial viability loss. In addition, the amorphous nano-Ta 2 O 5 coating can endow VO 2 with favorable cytocompatibility with human skin fibroblasts. This study may provide new insights into understanding the anti-biofouling and antimicrobial actions of amorphous transition metal oxide nanoparticles, which is conducive to expanding their potential applications in environmental fields.

Radiation-Induced Amorphization of Crystalline Ice

NASA Technical Reports Server (NTRS)

Fama, M.; Loeffler, M. J.; Raut, U.; Baragiola, R. A.

2009-01-01

We study radiation-induced amorphization of crystalline ice, ana lyzing the resu lts of three decades of experiments with a variety of projectiles, irradiation energy, and ice temperature, finding a similar trend of increasing resistance of amorphization with temperature and inconsistencies in results from different laboratories. We discuss the temperature dependence of amorphization in terms of the 'thermal spike' model. We then discuss the common use of the 1.65 micrometer infrared absorption band of water as a measure of degree of crystallinity, an increasingly common procedure to analyze remote sensing data of astronomical icy bodies. The discussion is based on new, high quality near-infrared refl ectance absorption spectra measured between 1.4 and 2.2 micrometers for amorphous and crystalline ices irradiated with 225 keV protons at 80 K. We found that, after irradiation with 10(exp 15) protons per square centimeter, crystalline ice films thinner than the ion range become fully amorphous, and that the infrared absorption spectra show no significant changes upon further irradiation. The complete amorphization suggests that crystalline ice observed in the outer Solar System, including trans-neptunian objects, may results from heat from internal sources or from the impact of icy meteorites or comets.

Anti-biofouling function of amorphous nano-Ta2O5 coating for VO2-based intelligent windows

NASA Astrophysics Data System (ADS)

Li, Jinhua; Guo, Geyong; Wang, Jiaxing; Zhou, Huaijuan; Shen, Hao; Yeung, Kelvin W. K.

2017-04-01

From environmental and health perspectives, the acquisition of a surface anti-biofouling property holds important significance for the usability of VO2 intelligent windows. Herein, we firstly deposited amorphous Ta2O5 nanoparticles on VO2 film by the magnetron sputtering method. It was found that the amorphous nano-Ta2O5 coating possessed a favorable anti-biofouling capability against Pseudomonas aeruginosa as an environmental microorganism model, behind which lay the mechanism that the amorphous nano-Ta2O5 could interrupt the microbial membrane electron transport chain and significantly elevate the intracellular reactive oxygen species (ROS) level. A plausible relationship was established between the anti-biofouling activity and physicochemical nature of amorphous Ta2O5 nanoparticles from the perspective of defect chemistry. ROS-induced oxidative damage gave rise to microbial viability loss. In addition, the amorphous nano-Ta2O5 coating can endow VO2 with favorable cytocompatibility with human skin fibroblasts. This study may provide new insights into understanding the anti-biofouling and antimicrobial actions of amorphous transition metal oxide nanoparticles, which is conducive to expanding their potential applications in environmental fields.

Novel Amorphous Fe-Zr-Si(Cu) Boron-free Alloys

NASA Astrophysics Data System (ADS)

Kopcewicz, M.; Grabias, A.; Latuch, J.; Kowalczyk, M.

2010-07-01

Novel amorphous Fe80(ZrxSi20-x-y)Cuy boron-free alloys, in which boron was completely replaced by silicon as a glass forming element, have been prepared in the form of ribbons by a melt quenching technique. The X-ray diffraction and Mössbauer spectroscopy measurements revealed that the as-quenched ribbons with the composition of x = 6-10 at. % and y = 0, 1 at. % are predominantly amorphous. DSC measurements allowed the estimation of the crystallization temperatures of the amorphous alloys. The soft magnetic properties have been studied by the specialized rf-Mössbauer technique in which the spectra were recorded during an exposure of the samples to the rf field of 0 to 20 Oe at 61.8 MHz. Since the rf-collapse effect observed is very sensitive to the local anisotropy fields it was possible to evaluate the soft magnetic properties of amorphous alloys studied. The rf-Mössbauer studies were accompanied by the conventional measurements of the quasi-static hysteresis loops from which the magnetization and coercive fields were estimated. It was found that amorphous Fe-Zr-Si(Cu) alloys are magnetically very soft, comparable with those of the conventional amorphous B-containing Fe-based alloys.

Indentation creep behaviors of amorphous Cu-based composite alloys

NASA Astrophysics Data System (ADS)

Song, Defeng; Ma, Xiangdong; Qian, Linfang

2018-04-01

This work reports the indentation creep behaviors of two Si2Zr3/amorphous Cu-based composite alloys utilizing nanoindentation technique. By analysis with Kelvin model, the retardation spectra of alloys at different positions, detached and attached regions to the intermetallics, were deduced. For the indentation of detached regions to Si2Zr3 intermetallics in both alloys, very similarity in creep displacement can be observed and retardation spectra show a distinct disparity in the second retardation peak. For the indentation of detached regions, the second retardation spectra also display distinct disparity. At both positions, the retardation spectra suggest that Si elements may lead to the relatively dense structure in the amorphous matrix and to form excessive Si2Zr3 intermetallics which may deteriorate the plastic deformation of current Cu-based composite alloys.

Graphene as a transparent electrode for amorphous silicon-based solar cells

NASA Astrophysics Data System (ADS)

Vaianella, F.; Rosolen, G.; Maes, B.

2015-06-01

The properties of graphene in terms of transparency and conductivity make it an ideal candidate to replace indium tin oxide (ITO) in a transparent conducting electrode. However, graphene is not always as good as ITO for some applications, due to a non-negligible absorption. For amorphous silicon photovoltaics, we have identified a useful case with a graphene-silica front electrode that improves upon ITO. For both electrode technologies, we simulate the weighted absorption in the active layer of planar amorphous silicon-based solar cells with a silver back-reflector. The graphene device shows a significantly increased absorbance compared to ITO-based cells for a large range of silicon thicknesses (34.4% versus 30.9% for a 300 nm thick silicon layer), and this result persists over a wide range of incidence angles.

Surface modification by carbon ion implantation for the application of ni-based amorphous alloys as bipolar plate in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Kim, Min-Uk; Kim, Do-Hyang; Han, Seung-hee; Fleury, Eric; Seok, Hyun-Kwang; Cha, Pil-Ryung; Kim, Yu-Chan

2011-04-01

Ni-based amorphous alloys with surface modification by carbon ion implantation are proposed as an alternative bipolar plate material for polymer electrolyte membrane fuel cells (PEMFCs). Both Ni60Nb20Ti10Zr10 alloys with and without carbon ion implantation have corrosion resistance as good as graphite as well as much lower contact resistance than 316L stainless steel in the PEMFC environment. The formation of conductive surface carbide due to carbon ion implantation results in a decrease in the contact resistance to a level comparable to that of graphite. This combination of excellent properties indicates that carbon ion implanted Ni-based amorphous alloys can be potential candidate materials for bipolar plates in PEMFCs.

Structures and mechanical behaviors of Zr55Cu35Al10 bulk amorphous alloys at ambient and cryogenic temperatures

NASA Astrophysics Data System (ADS)

Fan, Cang; Liaw, P. K.; Haas, V.; Wall, J. J.; Choo, H.; Inoue, A.; Liu, C. T.

2006-07-01

Based on a systematic study of pair distribution functions, carried out at cryogenic and ambient temperatures, on as-cast and crystallized ternary Zr-based bulk amorphous alloys (BAAs), we found that the atoms in BAAs are inhomogenously distributed at a local atomic level. They exist as different clusters with significantly shorter bond lengths than their crystallized counterpart structures—intermetallic compounds, and these structures exist stably in the amorphous state. This results in additional free volume, which is about ˜7% larger than that measured by the Archimedes method. The compressive strength measured at ˜77K was found to be ˜16% larger than that measured at 298K . In this study, an amorphous structural model is proposed, in which strongly bonded clusters acting as units are randomly distributed and strongly correlated to one another, as the free volume forms between clusters. Simulations with reverse Monte Carlo were performed by combining icosehadral and cubic structures as the initial structures for the BAA. The simulations show results consistent with our model. An attempt has been made to connect the relationship between amorphous structures and their mechanical properties.

Amorphous ZnO Quantum Dot/Mesoporous Carbon Bubble Composites for a High-Performance Lithium-Ion Battery Anode.

PubMed

Tu, Zhiming; Yang, Gongzheng; Song, Huawei; Wang, Chengxin

2017-01-11

Due to its high theoretical capacity (978 mA h g -1 ), natural abundance, environmental friendliness, and low cost, zinc oxide is regarded as one of the most promising anode materials for lithium-ion batteries (LIBs). A lot of research has been done in the past few years on this topic. However, hardly any research on amorphous ZnO for LIB anodes has been reported despite the fact that the amorphous type could have superior electrochemical performance due to its isotropic nature, abundant active sites, better buffer effect, and different electrochemical reaction details. In this work, we develop a simple route to prepare an amorphous ZnO quantum dot (QDs)/mesoporous carbon bubble composite. The composite consists of two parts: mesoporous carbon bubbles as a flexible skeleton and monodisperse amorphous zinc oxide QDs (smaller than 3 nm) encapsulated in an amorphous carbon matrix as a continuous coating tightly anchored on the surface of mesoporous carbon bubbles. With the benefits of abundant active sites, amorphous nature, high specific surface area, buffer effect, hierarchical pores, stable interconnected conductive network, and multidimensional electron transport pathways, the amorphous ZnO QD/mesoporous carbon bubble composite delivers a high reversible capacity of nearly 930 mA h g -1 (at current density of 100 mA g -1 ) with almost 90% retention for 85 cycles and possesses a good rate performance. This work opens the possibility to fabricate high-performance electrode materials for LIBs, especially for amorphous metal oxide-based materials.

New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

Electrochemical properties of rapidly solidified Si-Ti-Ni(-Cu) base anode for Li-ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Kwon, Hye Jin; Sohn, Keun Yong; Park, Won-Wook

2013-11-01

In this study, rapidly solidified Si-Ti-Ni-Cu alloys have been investigated as high capacity anodes for Li-ion secondary batteries. To obtain nano-sized Si particles dispersed in the inactive matrix, the alloy ribbons were fabricated using the melt spinning process. The thin ribbons were pulverized using ball-milling to make a fine powder of ˜ 4 µm average size. Coin-cell assembly was carried out under an argon gas in a glove box, in which pure lithium was used as a counter-electrode. The cells were cycled using the galvanostatic method in the potential range of 0.01 V and 1.5 V vs. Li/Li+. The microstructure and morphology were examined using an x-ray diffractometer, Field-Emission Scanning Electron Microscopy and High Resolution Transmission Electron Microscopy. Among the anode alloys, the Si70Ti15Ni15 electrodes had the highest discharge capacity (974.1 mAh/g) after the 50th cycle, and the Si60Ti16Ni16Cu8 electrode showed the best coulombic efficiency of ˜95.9% in cyclic behavior. It was revealed that the Si7Ni4Ti4 crystal phase coexisting with an amorphous phase, could more efficiently act as a buffer layer than the fully crystallized Si7Ni4Ti4 phase. Consequently, the electrochemical properties of the anode materials pronouncedly improved when the nano-sized primary Si particle was dispersed in the inactive Si7Ni4Ti4-based matrix mixed with an amorphous structure.

Nonpolar resistive memory switching with all four possible resistive switching modes in amorphous LaHoO{sub 3} thin films

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

Sharma, Yogesh; Pavunny, Shojan P.; Katiyar, Ram S., E-mail: rkatiyar@hpcf.upr.edu

2015-09-07

We studied the resistive memory switching in pulsed laser deposited amorphous LaHoO{sub 3} (a-LHO) thin films for non-volatile resistive random access memory applications. Nonpolar resistive switching (RS) was achieved in Pt/a-LHO/Pt memory cells with all four possible RS modes (i.e., positive unipolar, positive bipolar, negative unipolar, and negative bipolar) having high R{sub ON}/R{sub OFF} ratios (in the range of ∼10{sup 4}–10{sup 5}) and non-overlapping switching voltages (set voltage, V{sub ON} ∼ ±3.6–4.2 V and reset voltage, V{sub OFF} ∼ ±1.3–1.6 V) with a small variation of about ±5–8%. Temperature dependent current-voltage (I–V) characteristics indicated the metallic conduction in low resistance states (LRS). We believe that themore » formation (set) and rupture (reset) of mixed conducting filaments formed out of oxygen vacancies and metallic Ho atoms could be responsible for the change in the resistance states of the memory cell. Detailed analysis of I–V characteristics further corroborated the formation of conductive nanofilaments based on metal-like (Ohmic) conduction in LRS. Simmons-Schottky emission was found to be the dominant charge transport mechanism in the high resistance state.« less

Coherency strain and precipitation kinetics: crystalline and amorphous nitride formation in ternary Fe-Ti/Cr/V-Si alloys

NASA Astrophysics Data System (ADS)

Schwarz, B.; Rossi, P. J.; Straßberger, L.; Jörg, F.; Meka, S. R.; Bischoff, E.; Schacherl, R. E.; Mittemeijer, E. J.

2014-09-01

Specimens of iron-based binary Fe-Si alloy and ternary Fe-Me-Si alloys (with Me = Ti, Cr and V) were nitrided at 580 °C in a NH3/H2-gas mixture applying a nitriding potential of 0.1 atm-1/2 until nitrogen saturation in the specimens was attained. In contrast with recent observations in other Fe-Me1-Me2 alloys, no "mixed" (Me1, Me2) nitrides developed in Fe-Me-Si alloys upon nitriding: first, all Me precipitates as MeN; and thereafter, all Si precipitates as Si3N4. The MeN precipitates as crystalline, finely dispersed, nanosized platelets, obeying a Baker-Nutting orientation relationship (OR) with respect to the ferrite matrix. The Si3N4 precipitates as cubically, amorphous particles; the incoherent (part of the) MeN/α-Fe interface acts as heterogeneous nucleation site for Si3N4. The Si3N4-precipitation rate was found to be strongly dependent on the degree of coherency of the first precipitating MeN. The different, even opposite, kinetic effects observed for the various Fe-Me-Si alloys could be ascribed to the different time dependences of the coherent → incoherent transitions of the MeN particles in the different Fe-Me-Si alloys.

Biomimetic Deposition of Hydroxyapatite by Mixed Acid Treatment of Titanium Surfaces.

PubMed

Zhao, J M; Park, W U; Hwang, K H; Lee, J K; Yoon, S Y

2015-03-01

A simple chemical method was established for inducing bioactivity of Ti metal. In the present study, two kinds of mixed acid solutions were used to treat Ti specimens to induce Ca-P formation. Following a strong mixed acid activation process, Ca-P coatings successfully formed on the Ti surfaces in the simulated body fluid. Strong mixed acid etching was used to increase the roughness of the metal surface, because the porous and rough surfaces allow better adhesion between Ca-P coatings and substrate. Nano-scale modification of titanium surfaces can alter cellular and tissue responses, which may benefit osseointegration and dental implant therapy. Some specimens were treated with a 5 M NaOH aqueous solution, and then heat treated at 600 °C in order to form an amorphous sodium titanate layer on their surface. This treated titanium metal is believed to form a dense and uniform bone-like apatite layer on its surface in a simulated body fluid (SBF). This study proved that mixed acid treatment is not only important for surface passivation but is also another bioactive treatment for titanium surfaces, an alternative to alkali treatment. In addition, mixed acid treatment uses a lower temperature and shorter time period than alkali treatment.

Hydrogen trapping under the effect of W-C mixed layers

NASA Astrophysics Data System (ADS)

Liu, N.; Huang, J.; Sato, K.; Xu, Q.; Shi, L. Q.; Wang, Y. X.

2014-03-01

The retention of hydrogen (H) isotope in plasma-facing materials (PFMs) is an important issue for next step fusion device. We used density functional theory (DFT) to study the chemical bonds of H in tungsten-carbon (W-C) mixed layers of tungsten surface, aiming to explore the retention behaviour of H in PFMs. The solubility of C in W was first calculated for revealing the phase components in W-C mixed layers. It was found that C has low solubility in W, which prefers to be segregated on the W surface. Vacancies can enhance the solution of C in W. This makes C appear somewhat carbide feature. Thus, W-C mixed layers should contain multiple phase components. H retention strongly depends on the phase components in the W-C mixed layers. The solution of C will suppress the retention of H in W no matter whether neighbouring vacancies are present, or not. Hydrocarbon precursors, which were observed in desorption experiments, prefer to form by means of H binding to C atoms in C amorphous, or in precipitators in the W-C mixed layers, while not in tungsten carbide phase or in W bulk. Our investigation reasonably explains the experimental results.

Bio-Inspired Bright Structurally Colored Colloidal Amorphous Array Enhanced by Controlling Thickness and Black Background.

PubMed

Iwata, Masanori; Teshima, Midori; Seki, Takahiro; Yoshioka, Shinya; Takeoka, Yukikazu

2017-07-01

Inspired by Steller's jay, which displays angle-independent structural colors, angle-independent structurally colored materials are created, which are composed of amorphous arrays of submicrometer-sized fine spherical silica colloidal particles. When the colloidal amorphous arrays are thick, they do not appear colorful but almost white. However, the saturation of the structural color can be increased by (i) appropriately controlling the thickness of the array and (ii) placing the black background substrate. This is similar in the case of the blue feather of Steller's jay. Based on the knowledge gained through the biomimicry of structural colored materials, colloidal amorphous arrays on the surface of a black particle as the core particle are also prepared as colorful photonic pigments. Moreover, a structural color on-off system is successfully built by controlling the background brightness of the colloidal amorphous arrays. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous titanium-oxide supercapacitors.

PubMed

Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko

2016-10-21

The electric capacitance of an amorphous TiO 2-x surface increases proportionally to the negative sixth power of the convex diameter d. This occurs because of the van der Waals attraction on the amorphous surface of up to 7 mF/cm 2 , accompanied by extreme enhanced electron trapping resulting from both the quantum-size effect and an offset effect from positive charges at oxygen-vacancy sites. Here we show that a supercapacitor, constructed with a distributed constant-equipment circuit of large resistance and small capacitance on the amorphous TiO 2-x surface, illuminated a red LED for 37 ms after it was charged with 1 mA at 10 V. The fabricated device showed no dielectric breakdown up to 1,100 V. Based on this approach, further advances in the development of amorphous titanium-dioxide supercapacitors might be attained by integrating oxide ribbons with a micro-electro mechanical system.

Amorphous titanium-oxide supercapacitors

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Kuroda, Tomoyuki; Hasegawa, Fumihiko

2016-10-01

The electric capacitance of an amorphous TiO2-x surface increases proportionally to the negative sixth power of the convex diameter d. This occurs because of the van der Waals attraction on the amorphous surface of up to 7 mF/cm2, accompanied by extreme enhanced electron trapping resulting from both the quantum-size effect and an offset effect from positive charges at oxygen-vacancy sites. Here we show that a supercapacitor, constructed with a distributed constant-equipment circuit of large resistance and small capacitance on the amorphous TiO2-x surface, illuminated a red LED for 37 ms after it was charged with 1 mA at 10 V. The fabricated device showed no dielectric breakdown up to 1,100 V. Based on this approach, further advances in the development of amorphous titanium-dioxide supercapacitors might be attained by integrating oxide ribbons with a micro-electro mechanical system.

Enamel-like apatite crown covering amorphous mineral in a crayfish mandible

PubMed Central

Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara

2012-01-01

Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

Combining reactive sputtering and rapid thermal processing for synthesis and discovery of metal oxynitrides

DOE PAGES

Zhou, Lan; Suram, Santosh K.; Becerra-Stasiewicz, Natalie; ...

2015-05-27

Recent efforts have demonstrated enhanced tailoring of material functionality with mixed-anion materials, yet exploratory research with mixed-anion chemistries is limited by the sensitivity of these materials to synthesis conditions. In order to synthesize a particular metal oxynitride compound by traditional reactive annealing we require specific, limited ranges of both oxygen and nitrogen chemical potentials in order to establish equilibrium between the solid-state material and a reactive atmosphere. While using Ta-O-N as an example system, we describe a combination of reactive sputter deposition and rapid thermal processing for synthesis of mixed-anion inorganic materials. Heuristic optimization of reactive gas pressures to attainmore » a desired anion stoichiometry is discussed, and the ability of rapid thermal processing to enable amorphous to crystalline transitions without preferential anion loss is demonstrated through the controlled synthesis of nitride, oxide and oxynitride phases.« less

Parametric Study of Amorphous High-Entropy Alloys formation from two New Perspectives: Atomic Radius Modification and Crystalline Structure of Alloying Elements

NASA Astrophysics Data System (ADS)

Hu, Q.; Guo, S.; Wang, J. M.; Yan, Y. H.; Chen, S. S.; Lu, D. P.; Liu, K. M.; Zou, J. Z.; Zeng, X. R.

2017-01-01

Chemical and topological parameters have been widely used for predicting the phase selection in high-entropy alloys (HEAs). Nevertheless, previous studies could be faulted due to the small number of available data points, the negligence of kinetic effects, and the insensitivity to small compositional changes. Here in this work, 92 TiZrHfM, TiZrHfMM, TiZrHfMMM (M = Fe, Cr, V, Nb, Al, Ag, Cu, Ni) HEAs were prepared by melt spinning, to build a reliable and sufficiently large material database to inspect the robustness of previously established parameters. Modification of atomic radii by considering the change of local electronic environment in alloys, was critically found out to be superior in distinguishing the formation of amorphous and crystalline alloys, when compared to using atomic radii of pure elements in topological parameters. Moreover, crystal structures of alloying element were found to play an important role in the amorphous phase formation, which was then attributed to how alloying hexagonal-close-packed elements and face-centered-cubic or body-centered-cubic elements can affect the mixing enthalpy. Findings from this work not only provide parametric studies for HEAs with new and important perspectives, but also reveal possibly a hidden connection among some important concepts in various fields.

Nuclear magnetic resonance studies of DNP-ready trehalose obtained by solid state mechanochemical amorphization

NASA Astrophysics Data System (ADS)

Filibian, M.; Elisei, E.; Colombo Serra, S.; Rosso, A.; Tedoldi, F.; Cesàro, A.; Carretta, P.

$^1$H nuclear spin-lattice relaxation and Dynamic Nuclear Polarization (DNP) have been studied in amorphous samples of trehalose sugar doped with TEMPO radicals by means of mechanical milling, in the 1.6 K $\\div$ 4.2 K temperature range. The radical concentration was varied between 0.34 and 0.81 $\\%$. The highest polarization of 15 \\% at 1.6 K, observed in the sample with concentration $0.50 \\%$, is of the same order of magnitude of that reported in standard frozen solutions with TEMPO. The temperature and concentration dependence of the spin-lattice relaxation rate $1/T_{\\text{1}}$, dominated by the coupling with the electron spins, were found to follow power laws with an exponent close to $3$ in all samples. The observed proportionality between $1/T_{\\text{1}}$ and the polarization rate $1/T_{\\text{pol}}$, with a coefficient related to the electron polarization, is consistent with the presence of Thermal Mixing (TM) and a good contact between the nuclear and the electron spins. At high electron concentration additional relaxation channels causing a decrease in the nuclear polarization must be considered. These results provide further support for a more extensive use of amorphous DNP-ready samples, obtained by means of comilling, in dissolution DNP experiments and possibly for $\\textit{in vivo}$ metabolic imaging.

Nuclear magnetic resonance studies of DNP-ready trehalose obtained by solid state mechanochemical amorphization.

PubMed

Filibian, M; Elisei, E; Colombo Serra, S; Rosso, A; Tedoldi, F; Cesàro, A; Carretta, P

2016-06-22

(1)H nuclear spin-lattice relaxation and Dynamic Nuclear Polarization (DNP) have been studied in amorphous samples of trehalose sugar doped with TEMPO radicals by means of mechanical milling, in the 1.6-4.2 K temperature range. The radical concentration was varied between 0.34 and 0.81%. The highest polarization of 15% at 1.6 K, observed in the sample with concentration 0.50%, is of the same order of magnitude of that reported in standard frozen solutions with TEMPO. The temperature and concentration dependence of the spin-lattice relaxation rate 1/T1, dominated by the coupling with the electron spins, were found to follow power laws with an exponent close to 3 in all samples. The observed proportionality between 1/T1 and the polarization rate 1/Tpol, with a coefficient related to the electron polarization, is consistent with the presence of Thermal Mixing (TM) and a good contact between the nuclear and the electron spins. At high electron concentration additional relaxation channels causing a decrease in the nuclear polarization must be considered. These results provide further support for a more extensive use of amorphous DNP-ready samples, obtained by means of comilling, in dissolution DNP experiments and possibly for in vivo metabolic imaging.

Twinned Growth of Metal-Free, Triazine-Based Photocatalyst Films as Mixed-Dimensional (2D/3D) van der Waals Heterostructures.

PubMed

Schwarz, Dana; Noda, Yu; Klouda, Jan; Schwarzová-Pecková, Karolina; Tarábek, Ján; Rybáček, Jiří; Janoušek, Jiří; Simon, Frank; Opanasenko, Maksym V; Čejka, Jiří; Acharjya, Amitava; Schmidt, Johannes; Selve, Sören; Reiter-Scherer, Valentin; Severin, Nikolai; Rabe, Jürgen P; Ecorchard, Petra; He, Junjie; Polozij, Miroslav; Nachtigall, Petr; Bojdys, Michael J

2017-10-01

Design and synthesis of ordered, metal-free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed-dimensional (2D/3D) metal-free van der Waals (vdW) heterostructures based on triazine (C 3 N 3 ) linkers grow as large area, transparent yellow-orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E g,opt = 1.91 eV, E g,elec = 1.84 eV) and are moderately porous (124 m 2 g -1 ). The material consists of a crystalline 2D phase that is fully sp 2 hybridized and provides structural stability, and an amorphous, porous phase with mixed sp 2 -sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one-pot reaction mixture: unprecedented for metal-free frameworks and a direct consequence of on-catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal-free, light-induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h -1 g -1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of "wet" chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric Amorphous Solid Dispersions: A Review of Amorphization, Crystallization, Stabilization, Solid-State Characterization, and Aqueous Solubilization of Biopharmaceutical Classification System Class II Drugs.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-09-01

Poor water solubility of many drugs has emerged as one of the major challenges in the pharmaceutical world. Polymer-based amorphous solid dispersions have been considered as the major advancement in overcoming limited aqueous solubility and oral absorption issues. The principle drawback of this approach is that they can lack necessary stability and revert to the crystalline form on storage. Significant upfront development is, therefore, required to generate stable amorphous formulations. A thorough understanding of the processes occurring at a molecular level is imperative for the rational design of amorphous solid dispersion products. This review attempts to address the critical molecular and thermodynamic aspects governing the physicochemical properties of such systems. A brief introduction to Biopharmaceutical Classification System, solid dispersions, glass transition, and solubility advantage of amorphous drugs is provided. The objective of this review is to weigh the current understanding of solid dispersion chemistry and to critically review the theoretical, technical, and molecular aspects of solid dispersions (amorphization and crystallization) and potential advantage of polymers (stabilization and solubilization) as inert, hydrophilic, pharmaceutical carrier matrices. In addition, different preformulation tools for the rational selection of polymers, state-of-the-art techniques for preparation and characterization of polymeric amorphous solid dispersions, and drug supersaturation in gastric media are also discussed. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Composition-Dependent Morphology of Bi- and Trimetallic Phosphides: Construction of Amorphous Pd-Cu-Ni-P Nanoparticles as a Selective and Versatile Catalyst.

PubMed

Zhao, Ming; Ji, Yuan; Wang, Mengyue; Zhong, Ning; Kang, Zinan; Asao, Naoki; Jiang, Wen-Jie; Chen, Qiang

2017-10-11

Amorphous materials have been widely researched in heterogeneous catalysis and for next-generation batteries. However, the well-defined production of high-quality (e.g., monodisperse and high surface area) amorphous alloy nanomaterials has rarely been reported. In this work, we investigated the correlations among the composition, morphology, and catalysis of various Pd-M-P nanoparticles (NPs) (M = Cu or Ni), which indicated that less Cu (≤20 atom %) was necessary for the formation of an amorphous morphology. The amorphous Pd-Cu-Ni-P NPs were fabricated with a controllable size and characterized carefully, which show excellent selective catalysis in the semihydrogenation of alkynes, hydrogenation of quinoline, and oxidation of primary alcohols. The uniqueness of the catalytic performance was confirmed by control experiments with monometallic Pd, amorphous Pd-Ni-P NPs, crystalline Pd-Cu-P NPs, and a crystalline counterpart of Pd-Cu-Ni-P catalyst. The catalytic selectivity likely arose from improved Pd-M (M = Cu or Ni) synergistic effects in the amorphous phase and the electron deficiency of Pd. The model reactions proceeded under H 2 or O 2 gas without any additives, bases, or metal oxide supports, and the catalyst could be reused several times. This report is expected to shed light on the design of amorphous alloy nanomaterials as green and inexpensive catalysts for atom-economic and selective reactions.

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

Characterization of the temperature and humidity-dependent phase diagram of amorphous nanoscale organic aerosols.

PubMed

Rothfuss, Nicholas E; Petters, Markus D

2017-03-01

Atmospheric aerosols can exist in amorphous semi-solid or glassy phase states. These states are determined by the temperature (T) and relative humidity (RH). New measurements of viscosity for amorphous semi-solid nanometer size sucrose particles as a function of T and RH are reported. Viscosity is measured by inducing coagulation between two particles and probing the thermodynamic states that induce the particle to relax into a sphere. It is shown that the glass transition temperature can be obtained by extrapolation to 10 12 Pa s from the measured temperature-dependent viscosity in the 10 6 to 10 7 Pa s range. The experimental methodology was refined to allow isothermal probing of RH dependence and to increase the range of temperatures over which the dry temperature dependence can be studied. Several experiments where one monomer was sodium dodecyl sulfate (SDS), which remains solid at high RH, are also reported. These sucrose-SDS dimers were observed to relax into a sphere at T and RH similar to those observed in sucrose-sucrose dimers, suggesting that amorphous sucrose will flow over an insoluble particle at a viscosity similar to that characteristic of coalescence between two sucrose particles. Possible physical and analytical implications of this observation are considered. The data reported here suggest that semi-solid viscosity between 10 4 and 10 12 Pa s can be modelled over a wide range of T and RH using an adapted Vogel-Fulcher-Tammann equation and the Gordon-Taylor mixing rule. Sensitivity of modelled viscosity to variations in dry glass transition temperature, Gordon-Taylor constant, and aerosol hygroscopicity are explored, along with implications for atmospheric processes such as ice nucleation of glassy organic aerosols in the upper free troposphere. The reported measurement and modelling framework provides a template for characterizing the phase diagram of other amorphous aerosol systems, including secondary organic aerosols.

Amorphization of thiamine chloride hydrochloride: A study of the crystallization inhibitor properties of different polymers in thiamine chloride hydrochloride amorphous solid dispersions.

PubMed

Arioglu-Tuncil, Seda; Bhardwaj, Vivekanand; Taylor, Lynne S; Mauer, Lisa J

2017-09-01

Amorphous solid dispersions of thiamine chloride hydrochloride (THCl) were created using a variety of polymers with different physicochemical properties in order to investigate how effective the various polymers were as THCl crystallization inhibitors. THCl:polymer dispersions were prepared by lyophilizing solutions of THCl and amorphous polymers (guar gum, pectin, κ-carrageenan, gelatin, and polyvinylpyrrolidone (PVP)). These dispersions were stored at select temperature (25 and 40°C) and relative humidity (0, 23, 32, 54, 75, and 85% RH) conditions and monitored at different time points using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). Moisture sorption isotherms of all samples were also obtained. Initially amorphous THCl was produced in the presence of ≥40% w/w pectin, κ-carrageenan, gelatin, and guar gum or ≥60% w/w PVP. Trends in polymer THCl crystallization inhibition (pectin≥κ-carrageenan>gelatin>guar gum≫PVP) were primarily based on the ability of the polymer to interact with THCl via hydrogen bonding and/or ionic interactions. The onset of THCl crystallization from the amorphous dispersions was also related to storage conditions. THCl remained amorphous at low RH conditions (0 and 23% RH) in all 1:1 dispersions except THCl:PVP. THCl crystallized in some dispersions below the glass transition temperature (T g ) but remained amorphous in others at T~T g . At high RHs (75 and 85% RH), THCl crystallized within one day in all samples. Given the ease of THCl amorphization in the presence of a variety of polymers, even at higher vitamin concentrations than would be found in foods, it is likely that THCl is amorphous in many low moisture foods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spatial Distribution of Amorphization Intensity in Boron Carbide During Rate-Dependent Indentation and Impact Processes

NASA Astrophysics Data System (ADS)

Parsard, Gregory G.

Boron carbide is a lightweight ceramic commonly used in applications requiring high hardness. At sufficiently high stresses, the material experiences a localized phase transformation (amorphization) which seemingly weakens its structure. Raman spectroscopy is used to distinguish these transformed regions from crystalline material based on the evolution of new peaks in collected Raman spectra. Vickers indentations of various loads were created at quasistatic and dynamic strain rates to trigger amorphization. The resulting imprints and subsurface regions were scanned with Raman spectroscopy to map amorphization intensity at several depths to generate three-dimensional representations of the amorphized zones, which were analyzed to determine the influence of load and strain rate upon amorphized zone characteristics. The square of amorphized zone depth beneath Vickers indentations increases linearly with load and shows little to no strain rate dependence. Sudden decreases in amorphization intensity at certain depths coincided with the presence of lateral cracks, suggesting that lateral cracks may lead to a loss of amorphized material during mechanical polishing. Experimental results were compared against finite element simulations to estimate critical values of stress and strain associated with amorphization. Raman spectra were also analyzed to determine the indentation-induced residual compressive pressure in crystalline boron carbide. In unstressed crystalline boron carbide, a peak exists near 1088 cm-1 which shifts to higher wavenumbers with the application of compressive pressure. The change in position of this crystalline peak was tracked across surfaces at various depths beneath the indentations and then converted into pressure using the piezospectroscopic coefficient of boron carbide. Residual compressive pressures on the order of gigapascals were found near the indentations, with stress relaxation near regions affected by radial cracks, spall, and graphitic inclusions. These measured residual compressive pressures were consistently higher than those predicted by finite element simulations at various loads, suggesting that amorphization, which was not accounted for by the simulations, may increase compressive residual stress in the crystalline material. Amorphization may cause affected regions to expand relative to their formerly crystalline state and exerting radial compressive forces upon the surrounding crystalline regions and circumferential tension along its boundary, thus promoting crack propagation within the amorphized region.

Sol-gel formed spherical nanostructured titania based liquefied petroleum gas sensor

NASA Astrophysics Data System (ADS)

Sabhajeet, S. R.; Yadav, B. C.; Sonker, Rakesh K.

2018-05-01

The present work reports the preparation of Titania(TiO2) thin film by sol-gel technique and its Liquefied Petroleum Gas (LPG) sensing. TiO2 exists in numerous phases possessing different structural properties like amorphous, anatase or anatase/rutile mixed phases. The structural analysis confirmed the formation of TiO2 having an average crystallite size 21 nm. SEM showed the regular and porous surface morphology. The band gap of the material was found as 3.65 eV. This film was employed for LPG sensing and variations in resistance with exposure of LPG were observed. Sensor response (S) as a function of time was calculated and its maximum value was found as 2.8 for 4% vol. of LPG with a response and recovery times of 240 sec and 248 sec respectively.

Structural investigation and optical properties of xMnO2-25Li2O-5Na2O-15Bi2O3-(55-x)B2O3 glasses

NASA Astrophysics Data System (ADS)

Kulkarni, Shilpa; Jali, V. M.

2018-02-01

This paper deals with the new mixed system of glass compositions Lithium sodium bismuth borate glasses doped with transition metal oxide. The technique used to prepare a sample is by melt quenching. The XRD profile pattern confirmed the amorphous phase of the present glass system. The network structure is based on BO3, BO4 units and BiO6 octahedral units. No boroxyl rings observed in the glass structure. The addition of MnO2 in small amount does not account for major structural changes. Optical band gap lies in the range 1.89 to 0.96 eV. Density, molar volume, oxygen packing density, Tg, direct optical band gap and refractive index show anomalous behavior.

Microstructure and Electrochemical Behavior of Fe-Based Amorphous Metallic Coatings Fabricated by Atmospheric Plasma Spraying

NASA Astrophysics Data System (ADS)

Zhou, Z.; Wang, L.; He, D. Y.; Wang, F. C.; Liu, Y. B.

2011-01-01

A Fe48Cr15Mo14C15B6Y2 alloy with high glass forming ability (GFA) was selected to prepare amorphous metallic coatings by atmospheric plasma spraying (APS). The as-deposited coatings present a dense layered structure and low porosity. Microstructural studies show that some nanocrystals and a fraction of yttrium oxides formed during spraying, which induced the amorphous fraction of the coatings decreasing to 69% compared with amorphous alloy ribbons of the same component. High thermal stability enables the amorphous coatings to work below 910 K without crystallization. The results of electrochemical measurement show that the coatings exhibit extremely wide passive region and relatively low passive current density in 3.5% NaCl and 1 mol/L HCl solutions, which illustrate their superior ability to resist localized corrosion. Moreover, the corrosion behavior of the amorphous coatings in 1 mol/L H2SO4 solution is similar to their performance under conditions containing chloride ions, which manifests their flexible and extensive ability to withstand aggressive environments.

Fluxing purification and its effect on magnetic properties of high-Bs FeBPSiC amorphous alloy

NASA Astrophysics Data System (ADS)

Pang, Jing; Wang, Anding; Yue, Shiqiang; Kong, Fengyu; Qiu, Keqiang; Chang, Chuntao; Wang, Xinmin; Liu, Chain-Tsuan

2017-07-01

A high-Bs amorphous alloy with the base composition Fe83B11P3Si2C1 was used to study the effects of fluxing purification on amorphous forming ability and magnetic properties of the alloy prepared with raw materials in industrialization. By using fluxing purification, the surface crystallization was suppressed and fully amorphous Fe83B11P3Si2C1 ribbons with a maximum thickness of 48 μm were successfully achieved by using an industrial process and materials. The amorphous ribbons made with industrial-purified alloys exhibit excellent magnetic properties, containing high-Bs of 1.65 T, low Hc of 2.0 A/m, and high μe of 9.7 × 103 at 1 kHz. Impurities in the melting alloys exist in three forms and have different effluences on magnetic properties. The surface crystallization was triggered by the impurities which exist as high melting point inclusions serving as nuclei. Thus, fluxing purification is a feasible way for industrialization of high-Bs FeBPSiC amorphous alloys.

FIRST INFRARED BAND STRENGTHS FOR AMORPHOUS CO{sub 2}, AN OVERLOOKED COMPONENT OF INTERSTELLAR ICES

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

Gerakines, Perry A.; Hudson, Reggie L., E-mail: Reggie.Hudson@NASA.gov

2015-08-01

Solid carbon dioxide (CO{sub 2}) has long been recognized as a component of both interstellar and solar system ices, but a recent literature search has revealed significant qualitative and quantitative discrepancies in the laboratory spectra on which the abundances of extraterrestrial CO{sub 2} are based. Here we report new infrared (IR) spectra of amorphous CO{sub 2}-ice along with band intensities (band strengths) of four mid-IR absorptions, the first such results in the literature. A possible thickness dependence for amorphous-CO{sub 2} IR band shapes and positions also is investigated, and the three discordant reports of amorphous CO{sub 2} spectra in themore » literature are addressed. Applications of our results are discussed with an emphasis on laboratory investigations and results from astronomical observations. A careful comparison with earlier work shows that the IR spectra calculated from several databases for CO{sub 2} ices, all ices being made near 10 K, are not for amorphous CO{sub 2}, but rather for crystalline CO{sub 2} or crystalline-amorphous mixtures.« less

Preparation, mechanical strengths, and thermal

NASA Astrophysics Data System (ADS)

Inoue, A.; Furukawa, S.; Hagiwara, M.; Masumoto, T.

1987-05-01

Ni-based amorphous wires with good bending ductility have been prepared for Ni75Si8B17 and Ni78P12B10 alloys containing 1 to 2 at. pct Al or Zr by melt spinning in rotating water. The enhancement of the wire-formation tendency by the addition of Al has been clarified to be due to the increase in the stability of the melt jet through the formation of a thin A12O3 film on the outer surface. The maximum wire diameter is about 190 to 200 μm for the Ni-Si (or P)-B-Al alloys and increases to about 250 μm for the Ni-Si-B-Al-Cr alloys containing 4 to 6 at. pct Cr. The tensile fracture strength and fracture elongation are 2730 MPa and 2.9 pct for (Ni0.75Si0.08B0.17 99Al1) wire and 2170 MPa and 2.4 pct for (Ni0.78P0.12B0.1)99Al1 wire. These wires exhibit a fatigue limit under dynamic bending strain in air with a relative humidity of 65 pct; this limit is 0.50 pct for a Ni-Si-B-Al wire, which is higher by 0.15 pct than that of a Fe75Si10B15 amorphous wire. Furthermore, the Ni-base wires do not fracture during a 180-deg bending even for a sample annealed at temperatures just below the crystallization temperature, in sharp contrast to high embrittlement tendency for Fe-base amorphous alloys. Thus, the Ni-based amorphous wires have been shown to be an attractive material similar to Fe- and Co-based amorphous wires because of its high static and dynamic strength, high ductility, high stability to thermal embrittlement, and good corrosion resistance.

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.

The effect of processing on the surface physical stability of amorphous solid dispersions.

PubMed

Yang, Ziyi; Nollenberger, Kathrin; Albers, Jessica; Moffat, Jonathan; Craig, Duncan; Qi, Sheng

2014-11-01

The focus of this study was to investigate the effect of processing on the surface crystallization of amorphous molecular dispersions and gain insight into the mechanisms underpinning this effect. The model systems, amorphous molecular dispersions of felodipine-EUDRAGIT® E PO, were processed both using spin coating (an ultra-fast solvent evaporation based method) and hot melt extrusion (HME) (a melting based method). Amorphous solid dispersions with drug loadings of 10-90% (w/w) were obtained by both processing methods. Samples were stored under 75% RH/room temperatures for up to 10months. Surface crystallization was observed shortly after preparation for the HME samples with high drug loadings (50-90%). Surface crystallization was characterized by powder X-ray diffraction (PXRD), ATR-FTIR spectroscopy and imaging techniques (SEM, AFM and localized thermal analysis). Spin coated molecular dispersions showed significantly higher surface physical stability than hot melt extruded samples. For both systems, the progress of the surface crystal growth followed zero order kinetics on aging. Drug enrichment at the surfaces of HME samples on aging was observed, which may contribute to surface crystallization of amorphous molecular dispersions. In conclusion it was found the amorphous molecular dispersions prepared by spin coating had a significantly higher surface physical stability than the corresponding HME samples, which may be attributed to the increased process-related apparent drug-polymer solubility and reduced molecular mobility due to the quenching effect caused by the rapid solvent evaporation in spin coating. Copyright © 2014 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.

Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers.

PubMed

Davies, James F; Wilson, Kevin R

2016-02-16

The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. We present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D2O/H2O) to measure the water diffusion coefficient over a broad range (Dw ≈ 10(-12)-10(-17) m(2)·s(-1)) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO4). For the organic liquids in binary and ternary mixtures, Dw depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, Dw can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.

Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers

DOE PAGES

Davies, James F.; Wilson, Kevin R.

2016-01-11

The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. Here, we present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D 2O/H 2O) to measure the water diffusion coefficient over amore » broad range (D w ≈ 10 -12-10 -17 m 2s -1) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO 4). For the organic liquids in binary and ternary mixtures, D w depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO 4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, D w can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.« less

Resistance of fly ash-Portland cement blends to thermal shock

DOE PAGES

Pyatina, Tatiana; Sugama, Toshifumi

2015-09-11

Thermal-shock resistance of high-content fly ash-Portland cement blends was tested in the following ways. Activated and non-activated blends with 80-90 % fly ash F (FAF) were left to set at room temperature, then hydrated for 24 hours at 85°C and 24-more hours at 300°C and tested in five thermal-shock cycles (600°C heat - 25°C water quenching). XRD, and thermal gravimetric analyses, along with calorimetric measurements and SEM-EDX tests demonstrated that the activated blends form more hydrates after 24 hours at 300°C, and achieve a higher short-term compressive strength than do non-activated ones. Sodium meta-silicate and sodaash engendered the concomitant hydrationmore » of OPC and FAF, with the formation of mixed crystalline FAF-OPC hydrates and FAF hydrates, such as garranite, analcime, and wairakite, along with the amorphous FAF hydration products. In SS-activated and non-activated blends separate OPC (tobermorite) and FAF (amorphous gel) hydrates with no mixed crystalline products formed. The compressive strength of all tested blends decreased by nearly 50% after 5 thermal-shock test cycles. These changes in the compressive strength were accompanied by a marked decrease in the intensities of XRD patterns of the crystalline hydrates after the thermalshock. As a result, there was no significant difference in the performance of the blends with different activators« less

Amorphization of itraconazole by inorganic pharmaceutical excipients: comparison of excipients and processing methods.

PubMed

Grobelny, Pawel; Kazakevich, Irina; Zhang, Dan; Bogner, Robin

2015-01-01

The aim of this study was to investigate the effects of solid carriers and processing routes on the properties of amorphous solid dispersions of itraconazole. Three solid carriers with a range of surface properties were studied, (1) a mesoporous silicate, magnesium aluminum silicate (Neusilin US2), (2) a nonporous silicate of corresponding composition (Veegum) and (3) a non-silicate, inorganic excipient, calcium phosphate dibasic anhydrous (A-TAB). The drug was incorporated via either solvent-deposition or ball milling. Both the maximum drug deposited by solvent-based method that produced an amorphous composite and the time for complete amorphization by co-milling was determined by X-ray powder diffraction (XRPD). Changes in the drug and excipients were monitored by nitrogen adsorption and wettability of the powder. The ability of the excipients to amorphize the drug and enhance its dissolution was related to the powder characteristics. Neusilin provided the fastest amorphization time in the mill and highest drug loading by solvent-deposition, compared with the other two excipients. Solvent-deposition provided greater dissolution enhancement than milling, due to the reduction in Neusilin porosity during high energy milling.This study confirms that substrates as well as the processing routes have notable influence on the drug deposition, amorphization, physical stability and drug in vitro release.

Effect of ball milling on the physicochemical properties of atorvastatin calcium sesquihydrate: the dissolution kinetic behaviours of milled amorphous solids.

PubMed

Kobayashi, Makiko; Hattori, Yusuke; Sasaki, Tetsuo; Otsuka, Makoto

2017-01-01

The purposes of this study were to clarify the amorphization by ball milling of atorvastatin calcium sesquihydrate (AT) and to analyse the change in dissolution kinetics. The amorphous AT was prepared from crystal AT by ball milling and analysed in terms of the changes of its physicochemical properties by powder X-ray diffraction analysis (XRD), thermal analysis and infrared spectroscopy (IR). Moreover, to evaluate the usefulness of the amorphous form for pharmaceutical development, intrinsic solubility of the ground product was evaluated using a dissolution kinetic method. The XRD results indicated that crystalline AT was transformed into amorphous solids by more than 30-min milling. The thermal analysis result suggested that chemical potential of the ground AT are changed significantly by milling. The IR spectra of the AT showed the band shift from the amide group at 3406 cm -1 with an intermolecular hydrogen bond to a free amide group at 3365 cm -1 by milling. The dissolution of amorphous AT follows a dissolution kinetic model involving phase transformation. The initial dissolution rate of the ground product increased with the increase in milling time to reflect the increase in the intrinsic solubility based on the amorphous state. © 2016 Royal Pharmaceutical Society.

The plasma electrolytic oxidation micro-discharge channel model and its microstructure characteristic based on Ti tracer

NASA Astrophysics Data System (ADS)

Gao, Fangyuan; Hao, Li; Li, Guang; Xia, Yuan

2018-02-01

This study focuses on the individual discharge channel of ceramic coating prepared by plasma electrolytic oxidation (PEO), and attempts to reveal the mechanism of breakdown discharge at low voltage. Titanium (Ti) was employed as a substrate with the layer of aluminum deposited on it (aluminized Ti). The shape and microstructure of the discharge channels in PEO coatings were investigated using transmission electron microscope (TEM) and scanning electron microscopy (SEM). A schematic model of the individual discharge channel was proposed based on Ti tracer method. The shape of the discharge channel was mainly cylinder-shaped in the compact coating, with a groove-like oxidation region existed at the coating/substrate interface. In the groove-like oxidation region, the phase composition mainly composed of amorphous and mixed polycrystalline (aluminum titanate and mullite). β-Al2O3 was found in the ceramic coating. TEM morphology showed that nanometer sized micro channels existed in the ceramic coatings.

Strong enhancement in thermal conductivity of ethylene glycol-based nanofluids by amorphous and crystalline Al{sub 2}O{sub 3} nanoparticles

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

Gangwar, J.; Department of Physics, Panjab University, Chandigarh 160014; Srivastava, A. K., E-mail: aks@nplindia.org, E-mail: avanish.aks555@gmail.com

2014-08-11

In the present work, the temperature and concentration dependence of thermal conductivity (TC) enhancement in ethylene glycol (EG)-based amorphous and crystalline Al{sub 2}O{sub 3} nanofluids have been investigated at temperatures ranging from 0 to 100 °C. In our prior study, nanometer-sized particles of amorphous-, γ-, and α-Al{sub 2}O{sub 3} were prepared via a simple sol-gel process with annealing at different temperatures and characterized by various techniques. Building upon the earlier study, we probe here the crystallinity, microstructure, and morphology of the obtained α-Al{sub 2}O{sub 3} nanoparticles (NPs) by using X-ray powder diffraction with Rietveld full-profile refinement, scanning electron microscopy, and high-resolutionmore » transmission electron microscopy, respectively. In this study, we achieved a 74% enhancement in TC at higher temperature (100 °C) of base fluid EG by incorporating 1.0 vol. % of amorphous-Al{sub 2}O{sub 3}, whereas 52% and 37% enhancement is accomplished by adding γ- and α-Al{sub 2}O{sub 3} NPs, respectively. The amorphous phase of NPs appears to have good TC enhancement in nanofluids as compared to crystalline Al{sub 2}O{sub 3}. In a nutshell, these results are demonstrating the potential consequences of Al{sub 2}O{sub 3} NPs for applications of next-generation efficient energy transfer in nanofluids.« less

Interpretation of Fracture Toughness and R-Curve Behavior by Direct Observation of Microfracture Process in Ti-Based Dendrite-Containing Amorphous Alloys

NASA Astrophysics Data System (ADS)

Jeon, Changwoo; Kim, Choongnyun Paul; Kim, Hyoung Seop; Lee, Sunghak

2015-04-01

Fracture properties of Ti-based amorphous alloys containing ductile β dendrites were explained by directly observing microfracture processes. Three Ti-based amorphous alloys were fabricated by adding Ti, Zr, V, Ni, Al, and Be into a Ti-6Al-4V alloy by a vacuum arc melting method. The effective sizes of dendrites varied from 63 to 104 μm, while their volume fractions were almost constant within the range from 74 to 76 pct. The observation of the microfracture of the alloy containing coarse dendrites revealed that a microcrack initiated at the amorphous matrix of the notch tip and propagated along the amorphous matrix. In the alloy containing fine dendrites, the crack propagation was frequently blocked by dendrites, and many deformation bands were formed near or in front of the propagating crack, thereby resulting in a zig-zag fracture path. Crack initiation toughness was almost the same at 35 to 36 MPa√m within error ranges in the three alloys because it was heavily affected by the stress applied to the specimen at the time of crack initiation at the crack tip as well as strength levels of the alloys. According to the R-curve behavior, however, the best overall fracture properties in the alloy containing fine dendrites were explained by mechanisms of blocking of the crack growth and crack blunting and deformation band formation at dendrites.

New Approaches to the Computer Simulation of Amorphous Alloys: A Review.

PubMed

Valladares, Ariel A; Díaz-Celaya, Juan A; Galván-Colín, Jonathan; Mejía-Mendoza, Luis M; Reyes-Retana, José A; Valladares, Renela M; Valladares, Alexander; Alvarez-Ramirez, Fernando; Qu, Dongdong; Shen, Jun

2011-04-13

In this work we review our new methods to computer generate amorphous atomic topologies of several binary alloys: SiH, SiN, CN; binary systems based on group IV elements like SiC; the GeSe 2 chalcogenide; aluminum-based systems: AlN and AlSi, and the CuZr amorphous alloy. We use an ab initio approach based on density functionals and computationally thermally-randomized periodically-continued cells with at least 108 atoms. The computational thermal process to generate the amorphous alloys is the undermelt-quench approach, or one of its variants, that consists in linearly heating the samples to just below their melting (or liquidus) temperatures, and then linearly cooling them afterwards. These processes are carried out from initial crystalline conditions using short and long time steps. We find that a step four-times the default time step is adequate for most of the simulations. Radial distribution functions (partial and total) are calculated and compared whenever possible with experimental results, and the agreement is very good. For some materials we report studies of the effect of the topological disorder on their electronic and vibrational densities of states and on their optical properties.

New Approaches to the Computer Simulation of Amorphous Alloys: A Review

PubMed Central

Valladares, Ariel A.; Díaz-Celaya, Juan A.; Galván-Colín, Jonathan; Mejía-Mendoza, Luis M.; Reyes-Retana, José A.; Valladares, Renela M.; Valladares, Alexander; Alvarez-Ramirez, Fernando; Qu, Dongdong; Shen, Jun

2011-01-01

In this work we review our new methods to computer generate amorphous atomic topologies of several binary alloys: SiH, SiN, CN; binary systems based on group IV elements like SiC; the GeSe2 chalcogenide; aluminum-based systems: AlN and AlSi, and the CuZr amorphous alloy. We use an ab initio approach based on density functionals and computationally thermally-randomized periodically-continued cells with at least 108 atoms. The computational thermal process to generate the amorphous alloys is the undermelt-quench approach, or one of its variants, that consists in linearly heating the samples to just below their melting (or liquidus) temperatures, and then linearly cooling them afterwards. These processes are carried out from initial crystalline conditions using short and long time steps. We find that a step four-times the default time step is adequate for most of the simulations. Radial distribution functions (partial and total) are calculated and compared whenever possible with experimental results, and the agreement is very good. For some materials we report studies of the effect of the topological disorder on their electronic and vibrational densities of states and on their optical properties. PMID:28879948

Defects in Amorphous Semiconductors: The Case of Amorphous Indium Gallium Zinc Oxide

NASA Astrophysics Data System (ADS)

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

2018-05-01

Based on a rational classification of defects in amorphous materials, we propose a simplified model to describe intrinsic defects and hydrogen impurities in amorphous indium gallium zinc oxide (a -IGZO). The proposed approach consists of organizing defects into two categories: point defects, generating structural anomalies such as metal—metal or oxygen—oxygen bonds, and defects emerging from changes in the material stoichiometry, such as vacancies and interstitial atoms. Based on first-principles simulations, it is argued that the defects originating from the second group always act as perfect donors or perfect acceptors. This classification simplifies and rationalizes the nature of defects in amorphous phases. In a -IGZO, the most important point defects are metal—metal bonds (or small metal clusters) and peroxides (O - O single bonds). Electrons are captured by metal—metal bonds and released by the formation of peroxides. The presence of hydrogen can lead to two additional types of defects: metal-hydrogen defects, acting as acceptors, and oxygen-hydrogen defects, acting as donors. The impact of these defects is linked to different instabilities observed in a -IGZO. Specifically, the diffusion of hydrogen and oxygen is connected to positive- and negative-bias stresses, while negative-bias illumination stress originates from the formation of peroxides.

Ferrofluids based on Co-Fe-Si-B amorphous nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Tianqi; Bian, Xiufang; Yang, Chuncheng; Zhao, Shuchun; Yu, Mengchun

2017-03-01

Magnetic Co-Fe-Si-B amorphous nanoparticles were successfully synthesized by chemical reduction method. ICP, XRD, DSC, and TEM were used to investigate the composition, structure and morphology of Co-Fe-Si-B samples. The results show that the Co-Fe-Si-B samples are amorphous, which consist of nearly spherical nanoparticles with an average particle size about 23 nm. VSM results manifest that the saturation magnetization (Ms) of Co-Fe-Si-B samples ranges from 46.37 to 62.89 emu/g. Two kinds of ferrofluids (FFs) were prepared by dispersing Co-Fe-Si-B amorphous nanoparticles and CoFe2O4 nanoparticles in kerosene and silicone oil, respectively. The magnetic properties, stability and viscosity of the FFs were investigated. The FFs with Co-Fe-Si-B samples have a higher Ms and lower coercivity (Hc) than FFs with CoFe2O4 sample. Under magnetic field, the silicone oil-based FFs exhibit high stability. The viscosity of FFs under different applied magnetic fields was measured by a rotational viscometer, indicating that FFs with Co-Fe-Si-B particles present relative strong response to an external magnetic field. The metal-boride amorphous alloy nanoparticles have potential applications in the preparation of magnetic fluids with good stability and good magnetoviscous properties.

Synthesis and characterization of mesoporous ceria/alumina nanocomposite materials via mixing of the corresponding ceria and alumina gel precursors.

PubMed

Khalil, Kamal M S

2007-03-01

Mesoporous ceria/alumina, CeO(2)/Al(2)O(3), composites containing 10, 20 and 30% (w/w) ceria were prepared by a novel gel mixing method. In the method, ceria gel (formed via hydrolysis of ammonium cerium(IV) nitrate by aqueous ammonium carbonate solution) and alumina gel (formed via controlled hydrolysis of aluminum tri-isopropoxide) were mixed together. The mixed gel was subjected to subsequent drying and calcination for 3 h at 400, 600, 800 and 1000 degrees C. The uncalcined (dried at 110 degrees C) and the calcined composites were investigated by different techniques including TGA, DSC, FTIR, XRD, SEM and nitrogen adsorption/desorption isotherms. Results indicated that composites calcined for 3 h at 800 degrees C mainly kept amorphous alumina structure and gamma-alumina formed only upon calcinations at 1000 degrees C. On the other hand, CeO(2) was found to crystallize in the common ceria, cerinite, phase and it kept this structure over the entire calcination range (400-1000 degrees C). Therefore, high surface areas, stable surface textures, and non-aggregated nano-sized ceria dispersions were obtained. A systematic texture change based on ceria ratio was observed, however in all cases mesoporous composite materials exposing thermally stable texture and structure were obtained. The presented method produces composite ceria/alumina materials that suit different applications in the field of catalysis and membranes technology, and throw some light on physicochemical factors that determine textural morphology and thermal stability of such important composite.

Biodegradable materials based on silk fibroin and keratin.

PubMed

Vasconcelos, Andreia; Freddi, Giuliano; Cavaco-Paulo, Artur

2008-04-01

Wool and silk were dissolved and used for the preparation of blended films. Two systems are proposed: (1) blend films of silk fibroin and keratin aqueous solutions and (2) silk fibroin and keratin dissolved in formic acid. The FTIR spectra of pure films cast from aqueous solutions indicated that the keratin secondary structure mainly consists of alpha-helix and random coil conformations. The IR spectrum of pure SF is characteristic of films with prevalently amorphous structure (random coil conformation). Pure keratin film cast from formic acid shows an increase in the amount of beta-sheet and disordered keratin structures. The FTIR pattern of SF dissolved in formic acid is characteristic of films with prevalently beta-sheet conformations with beta-sheet crystallites embedded in an amorphous matrix. The thermal behavior of the blends confirmed the FTIR results. DSC curve of pure SF is typical of amorphous SF and the curve of pure keratin show the characteristic melting peak of alpha-helices for the aqueous system. These patterns are no longer observed in the films cast from formic acid due to the ability of formic acid to induce crystallization of SF and to increase the amount of beta-sheet structures on keratin. The nonlinear trend of the different parameters obtained from FTIR analysis and DSC curves of both SF/keratin systems indicate that when proteins are mixed they do not follow additives rules but are able to establish intermolecular interactions. Degradable polymeric biomaterials are preferred candidates for medical applications. It was investigated the degradation behavior of both SF/keratin systems by in vitro enzymatic incubation with trypsin. The SF/keratin films cast from water underwent a slower biological degradation than the films cast from formic acid. The weight loss obtained is a function of the amount of keratin in the blend. This study encourages the further investigation of the type of matrices presented here to be applied whether in scaffolds for tissue engineering or as controlled release drug delivery vehicles.

The effect of Se/Te ratio on transient absorption behavior and nonlinear absorption properties of CuIn0.7Ga0.3(Se1-xTex)2 (0 ≤ x ≤ 1) amorphous semiconductor thin films

NASA Astrophysics Data System (ADS)

Karatay, Ahmet; Küçüköz, Betül; Çankaya, Güven; Ates, Aytunc; Elmali, Ayhan

2017-11-01

The characterization of the CuInSe2 (CIS), CuInGaSe (CIGS) and CuGaSe2 (CGS) based semiconductor thin films are very important role for solar cell and various nonlinear optical applications. In this paper, the amorphous CuIn0.7Ga0.3(Se1-xTex)2 semiconductor thin films (0 ≤ x ≤ 1) were prepared with 60 nm thicknesses by using vacuum evaporation technique. The nonlinear absorption properties and ultrafast transient characteristics were investigated by using open aperture Z-scan and ultrafast pump-probe techniques. The energy bandgap values were calculated by using linear absorption spectra. The bandgap values are found to be varying from 0.67 eV to 1.25 eV for CuIn0.7Ga0.3Te2, CuIn0.7Ga0.3Se1.6Te0.4, CuIn0.7Ga0.3Se0.4Te1.6 and CuIn0.7Ga0.3Se2 thin films. The energy bandgap values decrease with increasing telluride (Te) doping ratio in mixed CuIn0.7Ga0.3(Se1-xTex)2 films. This affects nonlinear characteristics and ultrafast dynamics of amorphous thin films. Ultrafast pump-probe experiments indicated that decreasing of bandgap values with increasing the Te amount switches from the excited state absorption signals to ultrafast bleaching signals. Open aperture Z-scan experiments show that nonlinear absorption properties enhance with decreasing bandgaps values for 65 ps pulse duration at 1064 nm. Highest nonlinear absorption coefficient was found for CuIn0.7Ga0.3Te2 thin film due to having the smallest energy bandgap.

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.

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.

Growth of amorphous and epitaxial ZnSiP 2–Si alloys on Si

DOE PAGES

Martinez, Aaron D.; Miller, Elisa M.; Norman, Andrew G.; ...

2018-01-30

ZnSiP 2is a wide band gap material lattice matched with Si, with potential for Si-based optoelectronics. Here, amorphous ZnSiP 2–Si alloys are grown with tunable composition. Films with Si-rich compositions can be crystallized into epitaxial films.

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.

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.

Silylated functionalized silicon-based composite as anode with excellent cyclic performance for lithium-ion battery

NASA Astrophysics Data System (ADS)

Li, Xiao; Tian, Xiaodong; Yang, Tao; Wang, Wei; Song, Yan; Guo, Quangui; Liu, Zhanjun

2018-05-01

Inferior cycling stability and rate performance respectively caused by rigorous volume change and poor electrical conductivity were the main challenge of state-of-the-art Silicon-based electrode. In this work, silylated functionalized exfoliated graphite oxide (EGO)/silicon@amorphous carbon (3-APTS-EGO/Si@C) was synthesized by adopting silane as intermediate to connect Si particles with EGO sheets followed by introduction of amorphous carbon. The result suggested that 3-Aminopropyltriethoxysilan connected the EGO sheets and Si nanoparticles via covalent bonds. Owing to the strong covalent interaction and the synergistic effect between the silicon, EGO sheets and amorphous carbon, 3-APTS-EGO/Si@C composite possessed a high capacity of 774 mAh g-1 even after 450 cycles at 0.4 A g-1 with the retention capacity of 97%. This work also provided an effective strategy to improve the long cycling life performance of Si-based electrode.

Iron-Based Amorphous Metals: High-Performance Corrosion-Resistant Material Development

NASA Astrophysics Data System (ADS)

Farmer, Joseph; Choi, Jor-Shan; Saw, Cheng; Haslam, Jeffrey; Day, Dan; Hailey, Phillip; Lian, Tiangan; Rebak, Raul; Perepezko, John; Payer, Joe; Branagan, Daniel; Beardsley, Brad; D'Amato, Andy; Aprigliano, Lou

2009-06-01

An overview of the High-Performance Corrosion-Resistant Materials (HPCRM) Program, which was cosponsored by the Defense Advanced Research Projects Agency (DARPA) Defense Sciences Office (DSO) and the U.S. Department of Energy (DOE) Office of Civilian and Radioactive Waste Management (OCRWM), is discussed. Programmatic investigations have included a broad range of topics: alloy design and composition, materials synthesis, thermal stability, corrosion resistance, environmental cracking, mechanical properties, damage tolerance, radiation effects, and important potential applications. Amorphous alloys identified as SAM2X5 (Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4) and SAM1651 (Fe48Mo14Cr15Y2C15B6) have been produced as meltspun ribbons (MSRs), dropcast ingots, and thermal-spray coatings. Chromium (Cr), molybdenum (Mo), and tungsten (W) additions provided corrosion resistance, while boron (B) enabled glass formation. Earlier electrochemical studies of MSRs and ingots of these amorphous alloys demonstrated outstanding passive film stability. More recently, thermal-spray coatings of these amorphous alloys have been made and subjected to long-term salt-fog and immersion tests; good corrosion resistance has been observed during salt-fog testing. Corrosion rates were measured in situ with linear polarization, while the open-circuit corrosion potentials (OCPs) were simultaneously monitored; reasonably good performance was observed. The sensitivity of these measurements to electrolyte composition and temperature was determined. The high boron content of this particular amorphous metal makes this amorphous alloy an effective neutron absorber and suitable for criticality-control applications. In general, the corrosion resistance of such iron-based amorphous metals is maintained at operating temperatures up to the glass transition temperature. These materials are much harder than conventional stainless steel and Ni-based materials, and are proving to have excellent wear properties, sufficient to warrant their use in earth excavation, drilling, and tunnel-boring applications. Large areas have been successfully coated with these materials, with thicknesses of approximately 1 cm. The observed corrosion resistance may enable applications of importance in industries such as oil and gas production, refining, nuclear power generation, shipping, etc.

In situ TEM observation of preferential amorphization in single crystal Si nanowire

NASA Astrophysics Data System (ADS)

Su, Jiangbin; Zhu, Xianfang

2018-06-01

The nanoinstability of a single crystal Si nanowire under electron beam irradiation was in situ investigated at room temperature by the transmission electron microscopy technique. It was observed that the Si nanowire amorphized preferentially from the surface towards the center, with the increasing of the electron dose. In contrast, in the center of the Si nanowire the amorphization seemed much more difficult, being accompanied by the rotation of crystal grains and the compression of d-spacing. Such a preferential amorphization, which is athermally induced by the electron beam irradiation, can be well accounted for by our proposed concepts of the nanocurvature effect and the energetic beam-induced athermal activation effect, while the classical knock-on mechanism and the electron beam heating effect seem inadequate to explain these processes. Furthermore, the findings revealed the difference of amorphization between a Si nanowire and a Si film under electron beam irradiation. Also, the findings have important implications for the nanoinstability and nanoprocessing of future Si nanowire-based devices.

In situ TEM observation of preferential amorphization in single crystal Si nanowire.

PubMed

Su, Jiangbin; Zhu, Xianfang

2018-06-08

The nanoinstability of a single crystal Si nanowire under electron beam irradiation was in situ investigated at room temperature by the transmission electron microscopy technique. It was observed that the Si nanowire amorphized preferentially from the surface towards the center, with the increasing of the electron dose. In contrast, in the center of the Si nanowire the amorphization seemed much more difficult, being accompanied by the rotation of crystal grains and the compression of d-spacing. Such a preferential amorphization, which is athermally induced by the electron beam irradiation, can be well accounted for by our proposed concepts of the nanocurvature effect and the energetic beam-induced athermal activation effect, while the classical knock-on mechanism and the electron beam heating effect seem inadequate to explain these processes. Furthermore, the findings revealed the difference of amorphization between a Si nanowire and a Si film under electron beam irradiation. Also, the findings have important implications for the nanoinstability and nanoprocessing of future Si nanowire-based devices.

Structure and Properties of Amorphous Transparent Conducting Oxides

NASA Astrophysics Data System (ADS)

Medvedeva, Julia

Driven by technological appeal, the research area of amorphous oxide semiconductors has grown tremendously since the first demonstration of the unique properties of amorphous indium oxide more than a decade ago. Today, amorphous oxides, such as a-ITO, a-IZO, a-IGZO, or a-ZITO, exhibit the optical, electrical, thermal, and mechanical properties that are comparable or even superior to those possessed by their crystalline counterparts, pushing the latter out of the market. Large-area uniformity, low-cost low-temperature deposition, high carrier mobility, optical transparency, and mechanical flexibility make these materials appealing for next-generation thin-film electronics. Yet, the structural variations associated with crystalline-to-amorphous transition as well as their role in carrier generation and transport properties of these oxides are far from being understood. Although amorphous oxides lack grain boundaries, factors like (i) size and distribution of nanocrystalline inclusions; (ii) spatial distribution and clustering of incorporated cations in multicomponent oxides; (iii) formation of trap defects; and (iv) piezoelectric effects associated with internal strains, will contribute to electron scattering. In this work, ab-initio molecular dynamics (MD) and accurate density-functional approaches are employed to understand how the properties of amorphous ternary and quaternary oxides depend on quench rates, cation compositions, and oxygen stoichiometries. The MD results, combined with thorough experimental characterization, reveal that interplay between the local and long-range structural preferences of the constituent oxides gives rise to a complex composition-dependent structural behavior in the amorphous oxides. The proposed network models of metal-oxygen polyhedra help explain the observed intriguing electrical and optical properties in In-based oxides and suggest ways to broaden the phase space of amorphous oxide semiconductors with tunable properties. The work is supported by NSF-MRSEC program.

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

USGS Publications Warehouse

Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Room-temperature low-voltage electroluminescence in amorphous carbon nitride thin films

NASA Astrophysics Data System (ADS)

Reyes, R.; Legnani, C.; Ribeiro Pinto, P. M.; Cremona, M.; de Araújo, P. J. G.; Achete, C. A.

2003-06-01

White-blue electroluminescent emission with a voltage bias less than 10 V was achieved in rf sputter-deposited amorphous carbon nitride (a-CN) and amorphous silicon carbon nitride (a-SiCN) thin-film-based devices. The heterojunction structures of these devices consist of: Indium tin oxide (ITO), used as a transparent anode; amorphous carbon film as an emission layer, and aluminum as a cathode. The thickness of the carbon films was about 250 Å. In all of the produced diodes, a stable visible emission peaked around 475 nm is observed at room temperature and the emission intensity increases with the current density. For an applied voltage of 14 V, the luminance was about 3 mCd/m2. The electroluminescent properties of the two devices are discussed and compared.

Electroluminescence and transport properties in amorphous silicon nanostructures

NASA Astrophysics Data System (ADS)

Irrera, Alessia; Iacona, Fabio; Crupi, Isodiana; Presti, Calogero D.; Franzò, Giorgia; Bongiorno, Corrado; Sanfilippo, Delfo; Di Stefano, Gianfranco; Piana, Angelo; Fallica, Pier Giorgio; Canino, Andrea; Priolo, Francesco

2006-03-01

We report the results of a detailed study on the structural, electrical and optical properties of light emitting devices based on amorphous Si nanostructures. Amorphous nanostructures may constitute an interesting system for the monolithic integration of optical and electrical functions in Si ULSI technology. In fact, they exhibit an intense room temperature electroluminescence (EL), with the advantage of being formed at a temperature of 900 °C, while at least 1100 °C is needed for the formation of Si nanocrystals. Optical and electrical properties of amorphous Si nanocluster devices have been studied in the temperature range between 30 and 300 K. The EL is seen to have a bell-shaped trend as a function of temperature with a maximum at around 60 K. The efficiency of these devices is comparable to that found in devices based on Si nanocrystals, although amorphous nanostructures exhibit peculiar working conditions (very high current densities and low applied voltages). Time resolved EL measurements demonstrate the presence of a short lifetime, only partially due to the occurrence of non-radiative phenomena, since the very small amorphous clusters formed at 900 °C are characterized by a short radiative lifetime. By forcing a current through the device a phenomenon of charge trapping in the Si nanostructures has been observed. Trapped charges affect luminescence through an Auger-type non-radiative recombination of excitons. Indeed, it is shown that unbalanced injection of carriers (electrons versus holes) is one of the main processes limiting luminescence efficiency. These data will be reported and the advantages and limitations of this approach will be discussed.

Phosphate-bonded calcium aluminate cements

DOEpatents

Sugama, Toshifumi

1993-01-01

A method is described for making a rapid-setting phosphate-bonded cementitious material. A powdered aluminous cement is mixed with an aqueous solution of ammonium phosphate. The mixture is allowed to set to form an amorphous cementitious material which also may be hydrothermally treated at a temperature of from about 120.degree. C. to about 300.degree. C. to form a crystal-containing phosphate-bonded material. Also described are the cementitious products of this method and the cement composition which includes aluminous cement and ammonium polyphosphate.

Phosphate-bonded calcium aluminate cements

DOEpatents

Sugama, T.

1993-09-21

A method is described for making a rapid-setting phosphate-bonded cementitious material. A powdered aluminous cement is mixed with an aqueous solution of ammonium phosphate. The mixture is allowed to set to form an amorphous cementitious material which also may be hydrothermally treated at a temperature of from about 120 C to about 300 C to form a crystal-containing phosphate-bonded material. Also described are the cementitious products of this method and the cement composition which includes aluminous cement and ammonium polyphosphate. 10 figures.

Ultra-Small-Angle X-ray Scattering – X-ray Photon Correlation Spectroscopy Studies of Incipient Structural Changes in Amorphous Calcium Phosphate Based Dental Composites

PubMed Central

Zhang, F.; Allen, A.J.; Levine, L.E.; Espinal, L.; Antonucci, J.M.; Skrtic, D.; O’Donnell, J.N.R.; Ilavsky, J.

2012-01-01

The local structural changes in amorphous calcium phosphate (ACP) based dental composites were studied under isothermal conditions using both static, bulk measurement techniques and a recently developed methodology based on combined ultra-small angle X-ray scattering – X-ray photon correlation spectroscopy (USAXS-XPCS), which permits a dynamic approach. While results from conventional bulk measurements do not show clear signs of structural change, USAXS-XPCS results reveal unambiguous evidence for local structural variations on a similar time scale to that of water loss in the ACP fillers. A thermal-expansion based simulation indicates that thermal behavior alone does not account for the observed dynamics. Together, these results suggest that changes in the water content of ACP affect the composite morphology due to changes in ACP structure that occur without an amorphous-to-crystalline conversion. It is also noted that biomedical materials research could benefit greatly from USAXS-XPCS, a dynamic approach. PMID:22374649

Corrosion of low alloy steel containing 0.5% chromium in supercritical CO2-saturated brine and water-saturated supercritical CO2 environments

NASA Astrophysics Data System (ADS)

Wei, Liang; Gao, Kewei; Li, Qian

2018-05-01

The corrosion behavior of P110 low-Cr alloy steel in supercritical CO2-saturated brine (aqueous phase) and water-saturated supercritical CO2 (SC CO2 phase) was investigated. The results show that P110 steel primarily suffered general corrosion in the aqueous phase, while severe localized corrosion occurred in the SC CO2 phase. The formation of corrosion product scale on P110 steel in the aqueous phase divided into three stages: formation of the initial corrosion layer containing amorphous Cr(OH)3, FeCO3 and a small amount of Fe3C; transformation of initial corrosion layer to mixed layer, which consisted of FeCO3 and a small amount of Cr(OH)3 and Fe3C; growth and dissolution of the mixed layer. Finally, only a single mixed layer covered on the steel in the aqueous phase. However, the scale formed in SC CO2 phase consisted of two layers: the inner mixed layer and the dense outer FeCO3 crystalline layer.

Synthesis and characterization of lithium intercalation electrodes based on iron oxide thin films

NASA Astrophysics Data System (ADS)

Sarradin, J.; Guessous, A.; Ribes, M.

Sputter-deposited iron oxide thin films are investigated as a possible negative electrode for rocking-chair microbatteries. Experimental conditions related to the manufacturing of amorphous thin films suitable to a large number of available intercalation sites are described. Structural and physical properties of the thin layer films are presented. The conductivities of the amorphous thin films were found to be very high compared with those of the respective crystalline forms. Regarding the electrochemical behaviour, Fe 2O 3-based thin films electrodes are able to store and reversibly exchange lithium ions. At a C/2 charge/discharge rate with 100% depth-of-discharge (DOD), the specific capacity of these amorphous thin film electrodes remains almost constant and close to 330 Ah/kg after more than 120 charge/discharge cycles.

Variable-amplitude oscillatory shear response of amorphous materials.

PubMed

Perchikov, Nathan; Bouchbinder, Eran

2014-06-01

Variable-amplitude oscillatory shear tests are emerging as powerful tools to investigate and quantify the nonlinear rheology of amorphous solids, complex fluids, and biological materials. Quite a few recent experimental and atomistic simulation studies demonstrated that at low shear amplitudes, an amorphous solid settles into an amplitude- and initial-conditions-dependent dissipative limit cycle, in which back-and-forth localized particle rearrangements periodically bring the system to the same state. At sufficiently large shear amplitudes, the amorphous system loses memory of the initial conditions, exhibits chaotic particle motions accompanied by diffusive behavior, and settles into a stochastic steady state. The two regimes are separated by a transition amplitude, possibly characterized by some critical-like features. Here we argue that these observations support some of the physical assumptions embodied in the nonequilibrium thermodynamic, internal-variables based, shear-transformation-zone model of amorphous viscoplasticity; most notably that "flow defects" in amorphous solids are characterized by internal states between which they can make transitions, and that structural evolution is driven by dissipation associated with plastic deformation. We present a rather extensive theoretical analysis of the thermodynamic shear-transformation-zone model for a variable-amplitude oscillatory shear protocol, highlighting its success in accounting for various experimental and simulational observations, as well as its limitations. Our results offer a continuum-level theoretical framework for interpreting the variable-amplitude oscillatory shear response of amorphous solids and may promote additional developments.

Relationship between surface property and catalytic application of amorphous NiP/Hβ catalyst for n-hexane isomerization

NASA Astrophysics Data System (ADS)

Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

2017-12-01

The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.

Characterizing Amorphous Silicates in Extraterrestrial Materials

NASA Astrophysics Data System (ADS)

Fu, X.; Wang, A.; Krawczynski, M. J.

2015-12-01

Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the correlation between peak area ratio, A(500+700)/A1000, and NBO/T. In the 2nd step, we are synthesizing Mg-saponite using a sol-gel method. The crystallinity of sol-gel starting materials will be increased by a controlled hydrothermal treatment. The products will be characterized using XRD/TEM/Raman/NIR. The results will be reported at the conference.

Doubled heterogeneous crystal nucleation in sediments of hard sphere binary-mass mixtures

NASA Astrophysics Data System (ADS)

Löwen, Hartmut; Allahyarov, Elshad

2011-10-01

Crystallization during the sedimentation process of a binary colloidal hard spheres mixture is explored by Brownian dynamics computer simulations. The two species are different in buoyant mass but have the same interaction diameter. Starting from a completely mixed system in a finite container, gravity is suddenly turned on, and the crystallization process in the sample is monitored. If the Peclet numbers of the two species are both not too large, crystalline layers are formed at the bottom of the cell. The composition of lighter particles in the sedimented crystal is non-monotonic in the altitude: it is first increasing, then decreasing, and then increasing again. If one Peclet number is large and the other is small, we observe the occurrence of a doubled heterogeneous crystal nucleation process. First, crystalline layers are formed at the bottom container wall which are separated from an amorphous sediment. At the amorphous-fluid interface, a secondary crystal nucleation of layers is identified. This doubled heterogeneous nucleation can be verified in real-space experiments on colloidal mixtures.

In situ X-Ray Diffraction of Shock-Compressed Fused Silica

NASA Astrophysics Data System (ADS)

Tracy, Sally June; Turneaure, Stefan J.; Duffy, Thomas S.

2018-03-01

Because of its widespread applications in materials science and geophysics, SiO2 has been extensively examined under shock compression. Both quartz and fused silica transform through a so-called "mixed-phase region" to a dense, low compressibility high-pressure phase. For decades, the nature of this phase has been a subject of debate. Proposed structures include crystalline stishovite, another high-pressure crystalline phase, or a dense amorphous phase. Here we use plate-impact experiments and pulsed synchrotron x-ray diffraction to examine the structure of fused silica shock compressed to 63 GPa. In contrast to recent laser-driven compression experiments, we find that fused silica adopts a dense amorphous structure at 34 GPa and below. When compressed above 34 GPa, fused silica transforms to untextured polycrystalline stishovite. Our results can explain previously ambiguous features of the shock-compression behavior of fused silica and are consistent with recent molecular dynamics simulations. Stishovite grain sizes are estimated to be ˜5 - 30 nm for compression over a few hundred nanosecond time scale.

Innovative thermoplastic chitosan obtained by thermo-mechanical mixing with polyol plasticizers.

PubMed

Matet, Marie; Heuzey, Marie-Claude; Pollet, Eric; Ajji, Abdellah; Avérous, Luc

2013-06-05

Chitosan shows a degradation temperature lower than its melting point, which prevents its development in several applications. One way to overcome this issue is the plasticization of the carbohydrate. In this work plasticized chitosan was prepared by a thermo-mechanical kneading approach. The effects of different non-volatile polyol plasticizers (glycerol, xylitol and sorbitol) were investigated. The microstructure and morphology were determined using FTIR, XRD, TEM and SEM in order to understand the plasticization mechanism. Sorbitol, which is the highest molecular weight polyol used, resulted in plasticized chitosan with the highest thermal, mechanical and rheological properties. On the other hand, the sample plasticized with glycerol, the lowest molecular weight polyol, had the most important amorphous phase content and the lowest thermal, mechanical and rheological properties. Also, when the polyol content increased in the formulation, the plasticized chitosan was more amorphous and consequently its processability easier, while its properties decreased. Copyright © 2013 Elsevier Ltd. All rights reserved.

Long-term stable water vapor permeation barrier properties of SiN/SiCN/SiN nanolaminated multilayers grown by plasma-enhanced chemical vapor deposition at extremely low pressures

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

Choi, Bum Ho, E-mail: bhchoi@kitech.re.kr; Lee, Jong Ho

2014-08-04

We investigated the water vapor permeation barrier properties of 30-nm-thick SiN/SiCN/SiN nanolaminated multilayer structures grown by plasma enhanced chemical vapor deposition at 7 mTorr. The derived water vapor transmission rate was 1.12 × 10{sup −6} g/(m{sup 2} day) at 85 °C and 85% relative humidity, and this value was maintained up to 15 000 h of aging time. The X-ray diffraction patterns revealed that the nanolaminated film was composed of an amorphous phase. A mixed phase was observed upon performing high resolution transmission electron microscope analysis, which indicated that a thermodynamically stable structure was formed. It was revealed amorphous SiN/SiCN/SiN multilayer structures that are freemore » from intermixed interface defects effectively block water vapor permeation into active layer.« less

Surface and interface investigation of aluminosilicate biomaterial by the “in vivo” experiments

NASA Astrophysics Data System (ADS)

Oudadesse, H.; Derrien, A. C.; Martin, S.; Chaair, H.; Cathelineau, G.

2008-11-01

Porous mixtures of aluminosilicate/calcium phosphate have been studied for biomaterials applications. Aluminosilicates formed with an inorganic polymeric constitution present amorphous zeolites because of their 3D network structure and present the ability to link to bone matrix. Amorphous geopolymers of the potassium-poly(sialate)-nanopolymer type were synthesised at low temperature and studied for their use as potential biomaterials. They were mixed with 13% weight of calcium phosphate like biphasic hydroxyapatite and β-tricalcium phosphate. In this study, " in vivo" experiments were monitored to evaluate the biocompatibility, the surface and the interface behaviour of these composites when used as bone implants. Moreover, it has been demonstrated using histological and physicochemical studies that the developed materials exhibited a remarkable bone bonding when implanted in a rabbit's thighbone for a period of 1 month. The easy synthesis conditions (low temperature) of this composite and the fast intimate links with bone constitute an improvement of synthetic bone graft biomaterial.

Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

PubMed

Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

2014-10-01

Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques. Copyright © 2014 Elsevier Ltd. All rights reserved.

Outstanding visible photocatalytic activity of a new mixed bismuth titanatate material

NASA Astrophysics Data System (ADS)

Zambrano, P.; Sayagués, M. J.; Navío, J. A.; Hidalgo, M. C.

2017-02-01

In this work, a new photocatalyst based on bismuth titanates with outstanding visible photocatalytic activity was prepared by a facile hydrothermal method. The synthesised material showed visible activity as high as UV activity of commercial TiO2 P25 under the same experimental conditions for phenol degradation. A wide characterisation of the photocatalyst was performed. The material was composed of three phases; majority of Bi20TiO32 closely interconnected to Bi4Ti3O12 and amorphous TiO2. The high visible activity showed by this material could be ascribed to a combination of several features; i.e. low band gap energy value (2.1 eV), a structure allowing a good separation path for visible photogenerated electron-holes pairs and a relatively high surface area. This photocatalyst appeared as a promising material for solar and visible applications of photocatalysis.

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.

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.

Different amorphous solid-state forms of roxithromycin: A thermodynamic and morphological study.

PubMed

Milne, Marnus; Liebenberg, Wilna; Aucamp, Marique Elizabeth

2016-02-10

The striking impact that different preparation methods have on the characteristics of amorphous solid-state forms has attracted considerable attention during the last two decades. The pursuit of more extensive knowledge regarding polyamorphism therefore continues. The aim of this study was firstly, to investigate the influence of different preparation techniques to obtain amorphous solid-state forms for the same active pharmaceutical ingredient, namely roxithromycin. The preparation techniques also report on a method utilizing hot air, which although it is based on a melt intermediary step, is considered a novel preparation method. Secondly, to conduct an in-depth investigation into any physico-chemical differences between the resulting amorphous forms and thirdly, to bring our findings into context with that of previous work done, whilst simultaneously discussing a well-defined interpretation for the term polyamorphism and propose a discernment between true polyamorphism and pseudo-polyamorphism/atypical-polyamorphism. The preparation techniques included melt, solution, and a combination of solution-mechanical disruption as intermediary steps. The resulting amorphous forms were investigated using differential scanning calorimetry, X-ray powder diffraction, hot-stage microscopy, scanning electron microscopy, and vapor sorption. Clear and significant thermodynamic differences were determined between the four amorphous forms. It was also deduced from this study that different preparation techniques have a mentionable impact on the morphological properties of the resulting amorphous roxithromycin powders. Thermodynamic properties as well as the physical characteristics of the amorphous forms greatly governed other physico-chemical properties i.e. solubility and dissolution. Copyright © 2015 Elsevier B.V. All rights reserved.

Solubility advantage of amorphous pharmaceuticals: II. Application of quantitative thermodynamic relationships for prediction of solubility enhancement in structurally diverse insoluble pharmaceuticals.

PubMed

Murdande, Sharad B; Pikal, Michael J; Shanker, Ravi M; Bogner, Robin H

2010-12-01

To quantitatively assess the solubility advantage of amorphous forms of nine insoluble drugs with a wide range of physico-chemical properties utilizing a previously reported thermodynamic approach. Thermal properties of amorphous and crystalline forms of drugs were measured using modulated differential calorimetry. Equilibrium moisture sorption uptake by amorphous drugs was measured by a gravimetric moisture sorption analyzer, and ionization constants were determined from the pH-solubility profiles. Solubilities of crystalline and amorphous forms of drugs were measured in de-ionized water at 25°C. Polarized microscopy was used to provide qualitative information about the crystallization of amorphous drug in solution during solubility measurement. For three out the nine compounds, the estimated solubility based on thermodynamic considerations was within two-fold of the experimental measurement. For one compound, estimated solubility enhancement was lower than experimental value, likely due to extensive ionization in solution and hence its sensitivity to error in pKa measurement. For the remaining five compounds, estimated solubility was about 4- to 53-fold higher than experimental results. In all cases where the theoretical solubility estimates were significantly higher, it was observed that the amorphous drug crystallized rapidly during the experimental determination of solubility, thus preventing an accurate experimental assessment of solubility advantage. It has been demonstrated that the theoretical approach does provide an accurate estimate of the maximum solubility enhancement by an amorphous drug relative to its crystalline form for structurally diverse insoluble drugs when recrystallization during dissolution is minimal.

Generalized Slater--Pauling curve and the role of metalloids in Fe-based amorphous alloys

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

Sostarich, M.

1990-05-01

A modification of the generalized Slater--Pauling curve so as to consider the concentration dependence of the number of majority-spin {ital sp} electrons per average atom is proposed for amorphous iron-metalloid alloys. In this way an improved matching of the measured magnetic moment dependence on composition is achieved for Fe alloys with B and/or P as metalloids. Comparison of theory with experiment shows that amorphous Fe-P alloys tend to be magnetically rather strong, whereas their Fe-B counterparts are weak itinerant ferromagnets in almost the entire range of compositions.

β-relaxation related bright bands in thin film metallic glasses: Localized percolation of flow units captured via transmission electron microscope

NASA Astrophysics Data System (ADS)

Chen, Z. Q.; Huang, P.; Xu, K. W.; Wang, F.; Lu, T. J.

2016-12-01

We report that β-relaxation of amorphous NiW alloy film was effectively enhanced by adding two thin crystalline layers into the amorphous layer. Correspondingly, more bright bands, i.e., nano shear bands, were captured in the amorphous layer, which experienced more pronounced β-relaxations. Based on the potential energy landscape theory, the bright band was proposed to be the localized percolation of flow units corresponding to β-relaxation. Our findings may help connecting experimentally β-relaxation with flow units and shed light on the microstructure origin of β-relaxation.

A unified physical model of Seebeck coefficient in amorphous oxide semiconductor thin-film transistors

NASA Astrophysics Data System (ADS)

Lu, Nianduan; Li, Ling; Sun, Pengxiao; Banerjee, Writam; Liu, Ming

2014-09-01

A unified physical model for Seebeck coefficient was presented based on the multiple-trapping and release theory for amorphous oxide semiconductor thin-film transistors. According to the proposed model, the Seebeck coefficient is attributed to the Fermi-Dirac statistics combined with the energy dependent trap density of states and the gate-voltage dependence of the quasi-Fermi level. The simulation results show that the gate voltage, energy disorder, and temperature dependent Seebeck coefficient can be well described. The calculation also shows a good agreement with the experimental data in amorphous In-Ga-Zn-O thin-film transistor.

Recent Progress in Some Amorphous Materials for Supercapacitors.

PubMed

Li, Qing; Xu, Yuxia; Zheng, Shasha; Guo, Xiaotian; Xue, Huaiguo; Pang, Huan

2018-05-14

A breakthrough in technologies having "green" and sustainable energy storage conversion is urgent, and supercapacitors play a crucial role in this area of research. Owing to their unique porous structure, amorphous materials are considered one of the best active materials for high-performance supercapacitors due to their high specific capacity, excellent cycling stability, and fast charging rate. This Review summarizes the synthesis of amorphous materials (transition metal oxides, carbon-based materials, transition metal sulfides, phosphates, hydroxides, and their complexes) to highlight their electrochemical performance in supercapacitors. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shear Induced Structural Relaxation in a Supercooled Colloidal Liquid

NASA Astrophysics Data System (ADS)

Chen, Dandan; Semwogerere, Denis; Weeks, Eric R.

2009-11-01

Amorphous materials include many common products we use everyday, such as window glass, moisturizer, shaving cream and peanut butter. These materials have liquid-like disordered structure, but keep their shapes like a solid. The rheology of dense amorphous materials under large shear strain is not fully understood, partly due to the difficulty of directly viewing the microscopic details of such materials. We use a colloidal suspension to simulate amorphous materials, and study the shear- induced structural relaxation with fast confocal microscopy. We quantify the plastic rearrangements of the particles using standard analysis techniques based on the motion of the particles.

Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

DOEpatents

Farmer, Joseph C; Wong, Frank M.G.; Haslam, Jeffery J; Ji, Xiaoyan; Day, Sumner D; Blue, Craig A; Rivard, John D.K.; Aprigliano, Louis F; Kohler, Leslie K; Bayles, Robert; Lemieux, Edward J; Yang, Nancy; Perepezko, John H; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J

2013-09-03

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

DOEpatents

Farmer, Joseph C.; Wong, Frank M. G.; Haslam, Jeffery J.; Ji, Xiaoyan; Day, Sumner D.; Blue, Craig A.; Rivard, John D. K.; Aprigliano, Louis F.; Kohler, Leslie K.; Bayles, Robert; Lemieux, Edward J.; Yang, Nancy; Perepezko, John H.; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J.

2013-07-09

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

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.

Comparative study of structural, optical and impedance measurements on V{sub 2}O{sub 5} and V-Ce mixed oxide thin films

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

Malini, D. Rachel; Sanjeeviraja, C., E-mail: sanjeeviraja@rediffmail.com

Vanadium pentoxide (V{sub 2}O{sub 5}) and Vanadium-Cerium mixed oxide thin films at different molar ratios of V{sub 2}O{sub 5} and CeO{sub 2} have been deposited at 200 W rf power by rf planar magnetron sputtering in pure argon atmosphere. The structural and optical properties were studied by taking X-ray diffraction and transmittance and absorption spectra respectively. The amorphous thin films show an increase in transmittance and optical bandgap with increase in CeO{sub 2} content in as-prepared thin films. The impedance measurements for as-deposited thin films show an increase in electrical conductivity with increase in CeO{sub 2} material.

Synthesis Of Noble Metal Nanoparticle Composite Glasses Using Low Energy Ion Beam Mixing

NASA Astrophysics Data System (ADS)

Varma, Ranjana S.; Kothari, D. C.; Mahadkar, A. G.; Kulkarni, N. A.; Kanjilal, D.; Kumar, P.

2010-12-01

Carbon coated thin films of Cu or Au on fused silica glasses have been irradiated using 100 keV Ar+ ions at different fluences ranging from 1×1013 to 1×1016 ion/cm2. In this article, we explore a route to form noble metal nanoparticles in amorphous glass matrices without post irradiation annealing using low energy ion beam mixing where nuclear energy loss process is dominant. Optical and structural properties were studied using UV-Vis-NIR absorbance spectroscopy and Glancing angle X-ray Diffraction (GXRD). Results showed that Cu and Au nanoparticles are formed at higher fluence of 1×1016 ion/cm2 used in this work without annealing. The diameters of metal nanoparticles obtained from UV-Vis NIR and GXRD are in agreement.

Improvements in Microstructure and Wear Resistance of Plasma-Sprayed Fe-Based Amorphous Coating by Laser-Remelting

NASA Astrophysics Data System (ADS)

Jiang, Chaoping; Chen, Hong; Wang, Gui; Chen, Yongnan; Xing, Yazhe; Zhang, Chunhua; Dargusch, Matthew

2017-04-01

Amorphous coating technology is an attractive way of taking advantage of the superior properties of amorphous alloys for structural applications. However, the limited bonds between splats within the plasma-sprayed coatings result in a typically lamellar and porous coating structure. To overcome these limitations, the as-sprayed coating was treated by a laser-remelting process. The microstructure and phase composition of two coatings were analyzed using scanning electron microscopy with energy-dispersive spectroscopy, transmission electron microscopy, and x-ray diffraction. The wear resistance of the plasma-sprayed coating and laser-remelted coating was studied comparatively using a pin-on-disc wear test under dry friction conditions. It was revealed that the laser-remelted coating exhibited better wear resistance because of its defect-free and amorphous-nanocrystalline composited structure.

Substrate and Passivation Techniques for Flexible Amorphous Silicon-Based X-ray Detectors

PubMed Central

Marrs, Michael A.; Raupp, Gregory B.

2016-01-01

Flexible active matrix display technology has been adapted to create new flexible photo-sensing electronic devices, including flexible X-ray detectors. Monolithic integration of amorphous silicon (a-Si) PIN photodiodes on a flexible substrate poses significant challenges associated with the intrinsic film stress of amorphous silicon. This paper examines how altering device structuring and diode passivation layers can greatly improve the electrical performance and the mechanical reliability of the device, thereby eliminating one of the major weaknesses of a-Si PIN diodes in comparison to alternative photodetector technology, such as organic bulk heterojunction photodiodes and amorphous selenium. A dark current of 0.5 pA/mm2 and photodiode quantum efficiency of 74% are possible with a pixelated diode structure with a silicon nitride/SU-8 bilayer passivation structure on a 20 µm-thick polyimide substrate. PMID:27472329

Substrate and Passivation Techniques for Flexible Amorphous Silicon-Based X-ray Detectors.

PubMed

Marrs, Michael A; Raupp, Gregory B

2016-07-26

Flexible active matrix display technology has been adapted to create new flexible photo-sensing electronic devices, including flexible X-ray detectors. Monolithic integration of amorphous silicon (a-Si) PIN photodiodes on a flexible substrate poses significant challenges associated with the intrinsic film stress of amorphous silicon. This paper examines how altering device structuring and diode passivation layers can greatly improve the electrical performance and the mechanical reliability of the device, thereby eliminating one of the major weaknesses of a-Si PIN diodes in comparison to alternative photodetector technology, such as organic bulk heterojunction photodiodes and amorphous selenium. A dark current of 0.5 pA/mm² and photodiode quantum efficiency of 74% are possible with a pixelated diode structure with a silicon nitride/SU-8 bilayer passivation structure on a 20 µm-thick polyimide substrate.

A novel approach for analyzing glass-transition temperature vs. composition patterns: application to pharmaceutical compound+polymer systems.

PubMed

Kalogeras, Ioannis M

2011-04-18

In medicine, polymer-based materials are commonly used as excipients of poorly water-soluble drugs. The success of the encapsulation, as well as the physicochemical stability of the products, is often reflected on their glass transition temperature (T(g)) vs. composition (w) dependencies. The shape of the T(g)(w) patterns is critically influenced by polymer's molecular mass, drug molecule's shape and molecular volume, the type and degree of shielding of hydrogen-bonding capable functional groups, as well as aspects of the preparation process. By altering mixture's T(g) the amorphous solid form of the active ingredient may be retained at ambient or body temperatures, with concomitant improvements in handling, solubility, dissolution rate and oral bioavailability. Given the importance of the problem, the glass transitions observed in pharmaceutical mixtures have been extensively analyzed, aiming to appraise the state of mixing and intermolecular interactions. Here, accumulated experimental information on related systems is re-evaluated and comparably discussed under the light of a more effective and system-inclusive T(g)(w) equation. The present analysis indicates that free volume modifications and conformational changes of the macromolecular chains dominate, over enthalpic effects of mixing, in determining thermal characteristics and crystallization inhibition/retardation. Moreover, hydrogen-bonding and ion-dipole heterocontacts--although favorable of a higher degree of mixing--appear less significant compared to the steric hindrances and the antiplasticization proffered by the higher viscosity component. Copyright © 2011 Elsevier B.V. All rights reserved.

Solution-Processed Gallium–Tin-Based Oxide Semiconductors for Thin-Film Transistors

PubMed Central

Zhang, Xue; Lee, Hyeonju; Kim, Jungwon; Kim, Eui-Jik; Park, Jaehoon

2017-01-01

We investigated the effects of gallium (Ga) and tin (Sn) compositions on the structural and chemical properties of Ga–Sn-mixed (Ga:Sn) oxide films and the electrical properties of Ga:Sn oxide thin-film transistors (TFTs). The thermogravimetric analysis results indicate that solution-processed oxide films can be produced via thermal annealing at 500 °C. The oxygen deficiency ratio in the Ga:Sn oxide film increased from 0.18 (Ga oxide) and 0.30 (Sn oxide) to 0.36, while the X-ray diffraction peaks corresponding to Sn oxide significantly reduced. The Ga:Sn oxide film exhibited smaller grains compared to the nanocrystalline Sn oxide film, while the Ga oxide film exhibited an amorphous morphology. We found that the electrical properties of TFTs significantly improve by mixing Ga and Sn. Here, the optimum weight ratio of the constituents in the mixture of Ga and Sn precursor sols was determined to be 1.0:0.9 (Ga precursor sol:Sn precursor sol) for application in the solution-processed Ga:Sn oxide TFTs. In addition, when the Ga(1.0):Sn(0.9) oxide film was thermally annealed at 900 °C, the field-effect mobility of the TFT was notably enhanced from 0.02 to 1.03 cm2/Vs. Therefore, the mixing concentration ratio and annealing temperature are crucial for the chemical and morphological properties of solution-processed Ga:Sn oxide films and for the TFT performance. PMID:29283408

Spatial correlations and exact solution of the problem of the boson peak profile in amorphous media

NASA Astrophysics Data System (ADS)

Kirillov, Sviatoslav A.; A. Voyiatzis, George; Kolomiyets, Tatiana M.; H. Anastasiadis, Spiros

1999-11-01

Based on a model correlation function which covers spatial correlations from Gaussian to exponential, we have arrived at an exact analytic solution of the problem of the Boson peak profile in amorphous media. Probe fits made for polyisoprene and triacetin prove the working ability of the formulae obtained.

Kit systems for granulated decontamination formulations

DOEpatents

Tucker, Mark D.

2010-07-06

A decontamination formulation and method of making that neutralizes the adverse health effects of both chemical and biological compounds, especially chemical warfare (CW) and biological warfare (BW) agents, and toxic industrial chemicals. The formulation provides solubilizing compounds that serve to effectively render the chemical and biological compounds, particularly CW and BW compounds, susceptible to attack, and at least one reactive compound that serves to attack (and detoxify or kill) the compound. The formulation includes at least one solubilizing agent, a reactive compound, a sorbent additive, and water. A highly adsorbent sorbent additive (e.g., amorphous silica, sorbitol, mannitol, etc.) is used to "dry out" one or more liquid ingredients into a dry, free-flowing powder that has an extended shelf life, and is more convenient to handle and mix in the field. The formulation can be pre-mixed and pre-packaged as a multi-part kit system, where one or more of the parts are packaged in a powdered, granulated form for ease of handling and mixing in the field.

Superconductivity in ion-beam-mixed layered Au-Si thin films

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

Jisrawi, N.M.; McLean, W.L.; Stoffel, N.G.

The superconducting properties of thin films made by mixing alternating layers of Au and Si using ion-beam bombardment correlate with the formation of metastable metallic phases in what is otherwise a simple eutectic system. Transmission-electron-microscopy measurements reveal the superconducting phases to be amorphous. Compound formation and the nature of Au-Si bonding in these metastable phases are demonstrated from x-ray photoelectron spectroscopy and from a previous study of x-ray-absorption spectroscopy. After mixing with a beam of Xe ions, multilayered films with an average nominal composition Au{sub {ital x}}Si{sub 1{minus}{ital x}}, where {ital x}=0.2, 0.4, 0.5, 0.72, and 0.8, exhibited superconducting transitionmore » temperatures in the range 0.2--1.2 K. A double transition feature in the magnetic field dependence of the resistivity is attributed to the formation of more than one metastable metallic phase in the same sample as the ion dose increases.« less

Mechanical properties of cement concrete composites containing nano-metakaolin

NASA Astrophysics Data System (ADS)

Supit, Steve Wilben Macquarie; Rumbayan, Rilya; Ticoalu, Adriana

2017-11-01

The use of nano materials in building construction has been recognized because of its high specific surface area, very small particle sizes and more amorphous nature of particles. These characteristics lead to increase the mechanical properties and durability of cement concrete composites. Metakaolin is one of the supplementary cementitious materials that has been used to replace cement in concrete. Therefore, it is interesting to investigate the effectiveness of metakaolin (in nano scale) in improving the mechanical properties including compressive strength, tensile strength and flexural strength of cement concretes. In this experiment, metakaolin was pulverized by using High Energy Milling before adding to the concrete mixes. The pozzolan Portland cement was replaced with 5% and 10% nano-metakaolin (by wt.). The result shows that the optimum amount of nano-metakaolin in cement concrete mixes is 10% (by wt.). The improvement in compressive strength is approximately 123% at 3 days, 85% at 7 days and 53% at 28 days, respectively. The tensile and flexural strength results also showed the influence of adding 10% nano-metakaolin (NK-10) in improving the properties of cement concrete (NK-0). Furthermore, the Backscattered Electron images and X-Ray Diffraction analysis were evaluated to support the above findings. The results analysis confirm the pores modification due to nano-metakaolin addition, the consumption of calcium hydroxide (CH) and the formation of Calcium Silicate Hydrate (CSH) gel as one of the beneficial effects of amorphous nano-metakaolin in improving the mechanical properties and densification of microstructure of mortar and concrete.

Initial Drug Dissolution from Amorphous Solid Dispersions Controlled by Polymer Dissolution and Drug-Polymer Interaction.

PubMed

Chen, Yuejie; Wang, Shujing; Wang, Shan; Liu, Chengyu; Su, Ching; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Qian, Feng

2016-10-01

To identify the key formulation factors controlling the initial drug and polymer dissolution rates from an amorphous solid dispersion (ASD). Ketoconazole (KTZ) ASDs using PVP, PVP-VA, HMPC, or HPMC-AS as polymeric matrix were prepared. For each drug-polymer system, two types of formulations with the same composition were prepared: 1. Spray dried dispersion (SDD) that is homogenous at molecular level, 2. Physical blend of SDD (80% drug loading) and pure polymer (SDD-PB) that is homogenous only at powder level. Flory-Huggins interaction parameters (χ) between KTZ and the four polymers were obtained by Flory-Huggins model fitting. Solution (13)C NMR and FT-IR were conducted to investigate the specific drug-polymer interaction in the solution and solid state, respectively. Intrinsic dissolution of both the drug and the polymer from ASDs were studied using a Higuchi style intrinsic dissolution apparatus. PXRD and confocal Raman microscopy were used to confirm the absence of drug crystallinity on the tablet surface before and after dissolution study. In solid state, KTZ is completely miscible with PVP, PVP-VA, or HPMC-AS, demonstrated by the negative χ values of -0.36, -0.46, -1.68, respectively; while is poorly miscible with HPMC shown by a positive χ value of 0.23. According to solution (13)C NMR and FT-IR studies, KTZ interacts with HPMC-AS strongly through H-bonding and dipole induced interaction; with PVPs and PVP-VA moderately through dipole-induced interactions; and with HPMC weakly without detectable attractive interaction. Furthermore, the "apparent" strength of drug-polymer interaction, measured by the extent of peak shift on NMR or FT-IR spectra, increases with the increasing number of interacting drug-polymer pairs. For ASDs with the presence of considerable drug-polymer interactions, such as KTZ/PVPs, KTZ/PVP-VA, or KTZ /HPMC-AS systems, drug released at the same rate as the polymer when intimate drug-polymer mixing was ensured (i.e., the SDD systems); while drug released much slower than the polymer when molecular level mixing or drug-polymer interaction was absent (SDD-PB systems). For ASDs without drug-polymer interaction (i.e., KTZ/HPMC systems), the mixing homogeneity had little impact on the release rate of either the drug or the polymer thus SDD and SDD-PB demonstrated the same drug or polymer release rate, while the drug released slowly and independently of polymer release. The initial drug release from an ASD was controlled by 1) the polymer release rate; 2) the strength of drug-polymer interaction, including the intrinsic interaction caused by the chemistry of the drug and the polymer (measured by the χ value), as well as that the apparent interaction caused by the drug-polymer ratio (measure by the extent of peak shift on spectroscopic analysis); and 3) the level of mixing homogeneity between the drug and polymer. In summary, the selection of polymer, drug-polymer ratio, and ASD processing conditions have profound impacts on the dissolution behavior of ASDs. Graphical Abstract Relationship between initial drug and polymer dissolution rates from amorphous solid dispersions with different mixing uniformity and drug-polymer interactions.

Near single-crystalline, high-carrier-mobility silicon thin film on a polycrystalline/amorphous substrate

DOEpatents

Findikoglu, Alp T [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM; Arendt, Paul N [Los Alamos, NM; Matias, Vladimir [Santa Fe, NM; Choi, Woong [Los Alamos, NM

2009-10-27

A template article including a base substrate including: (i) a base material selected from the group consisting of polycrystalline substrates and amorphous substrates, and (ii) at least one layer of a differing material upon the surface of the base material; and, a buffer material layer upon the base substrate, the buffer material layer characterized by: (a) low chemical reactivity with the base substrate, (b) stability at temperatures up to at least about 800.degree. C. under low vacuum conditions, and (c) a lattice crystal structure adapted for subsequent deposition of a semiconductor material; is provided, together with a semiconductor article including a base substrate including: (i) a base material selected from the group consisting of polycrystalline substrates and amorphous substrates, and (ii) at least one layer of a differing material upon the surface of the base material; and, a buffer material layer upon the base substrate, the buffer material layer characterized by: (a) low chemical reactivity with the base substrate, (b) stability at temperatures up to at least about 800.degree. C. under low vacuum conditions, and (c) a lattice crystal structure adapted for subsequent deposition of a semiconductor material, and, a top-layer of semiconductor material upon the buffer material layer.

A molecular dynamics approach for predicting the glass transition temperature and plasticization effect in amorphous pharmaceuticals.

PubMed

Gupta, Jasmine; Nunes, Cletus; Jonnalagadda, Sriramakamal

2013-11-04

The objectives of this study were as follows: (i) To develop an in silico technique, based on molecular dynamics (MD) simulations, to predict glass transition temperatures (Tg) of amorphous pharmaceuticals. (ii) To computationally study the effect of plasticizer on Tg. (iii) To investigate the intermolecular interactions using radial distribution function (RDF). Amorphous sucrose and water were selected as the model compound and plasticizer, respectively. MD simulations were performed using COMPASS force field and isothermal-isobaric ensembles. The specific volumes of amorphous cells were computed in the temperature range of 440-265 K. The characteristic "kink" observed in volume-temperature curves, in conjunction with regression analysis, defined the Tg. The MD computed Tg values were 367 K, 352 K and 343 K for amorphous sucrose containing 0%, 3% and 5% w/w water, respectively. The MD technique thus effectively simulated the plasticization effect of water; and the corresponding Tg values were in reasonable agreement with theoretical models and literature reports. The RDF measurements revealed strong hydrogen bond interactions between sucrose hydroxyl oxygens and water oxygen. Steric effects led to weak interactions between sucrose acetal oxygens and water oxygen. MD is thus a powerful predictive tool for probing temperature and water effects on the stability of amorphous systems during drug development.

Effects of crystallization on structural and dielectric properties of thin amorphous films of (1 - x)BaTiO3-xSrTiO3 (x=0-0.5, 1.0)

NASA Astrophysics Data System (ADS)

Kawano, H.; Morii, K.; Nakayama, Y.

1993-05-01

The possibilities for fabricating solid solutions of (Ba1-x,Srx)TiO3 (x≤0.5,1.0) by crystallization of amorphous films and for improving their dielectric properties by adjusting the Sr content were investigated. Thin amorphous films were prepared from powder targets consisting of mixtures of BaTiO3 and SrTiO3 by sputtering with a neutralized Ar-ion beam. The amorphous films crystallized into (Ba1-x, Srx)TiO3 solid solutions with a cubic perovskite-type structure after annealing in air at 923 K for more than 1 h. The Debye-type dielectric relaxation was observed for the amorphous films, whereas the crystallized films showed paraelectric behavior. The relative dielectric constants were of the order of 20 for the amorphous samples, but increased greatly after crystallization to about 60-200, depending on the composition; a larger increase in the dielectric constant was observed in the higher Sr content films, in the range x≤0.5, which could be correlated with an increase in the grain size of the crystallites. The crystallization processes responsible for the difference in the grain size are discussed based on the microstructural observations.

Synthesis and Electrochemical Properties of Amorphous Carbon Coated Sn Anode Material for Lithium Ion Batteries and Sodium Ion Batteries.

PubMed

Choi, Ji-Seub; Lee, Hoi-Jin; Ha, Jong-Keun; Cho, Kwon-Koo

2018-09-01

Sn is one of the promising anode material for lithium-ion and sodium-ion batteries because of Sn has many advantages such as a high theoretical capacity of 994 mAh/g, inexpensive, abundant and nontoxic. However, Sn-based anodes have a critical problem from pulverization of the particles due to large volume change (>300% in lithium-ion battery and 420% in the sodium-ion battery) during alloying/dealloying reaction. To overcome this problem, we fabricate Sn/C particle of core/shell structure. Sn powder was produced by pulsed wire explosion in liquid media, and amorphous carbon coating process was prepared by hydrothermal synthesis. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 413 mAh/g and 452 mAh/g after 40 cycles in lithium half-cell test. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 240 mAh/g and 487 mAh/g after 40 cycles in sodium half-cell test. Amorphous carbon coating contributed to the improvement of capacity in lithium and sodium battery systems. And the effect of amorphous carbon coating in sodium battery system was superior to that in lithium battery system.

Amorphous InGaMgO Ultraviolet Photo-TFT with Ultrahigh Photosensitivity and Extremely Large Responsivity

PubMed Central

Zhang, Yiyu; Qian, Ling-Xuan; Wu, Zehan; Liu, Xingzhao

2017-01-01

Recently, amorphous InGaZnO ultraviolet photo thin-film transistors have exhibited great potential for application in future display technologies. Nevertheless, the transmittance of amorphous InGaZnO (~80%) is still not high enough, resulting in the relatively large sacrifice of aperture ratio for each sensor pixel. In this work, the ultraviolet photo thin-film transistor based on amorphous InGaMgO, which processes a larger bandgap and higher transmission compared to amorphous InGaZnO, was proposed and investigated. Furthermore, the effects of post-deposition annealing in oxygen on both the material and ultraviolet detection characteristics of amorphous InGaMgO were also comprehensively studied. It was found that oxygen post-deposition annealing can effectively reduce oxygen vacancies, leading to an optimized device performance, including lower dark current, higher sensitivity, and larger responsivity. We attributed it to the combined effect of the reduction in donor states and recombination centers, both of which are related to oxygen vacancies. As a result, the 240-min annealed device exhibited the lowest dark current of 1.7 × 10−10 A, the highest photosensitivity of 3.9 × 106, and the largest responsivity of 1.5 × 104 A/W. Therefore, our findings have revealed that amorphous InGaMgO photo thin-film transistors are a very promising alternative for UV detection, especially for application in touch-free interactive displays. PMID:28772529

Molecular dynamics simulations of Li transport between cathode crystals

NASA Astrophysics Data System (ADS)

Garofalini, S. H.

The molecular dynamics (MD) computer simulation technique has been used to study the effect of an amorphous intergranular film (IGF) present in a polycrystalline cathode on Li transport. The solid electrolyte is a model lithium silicate glass while the cathode is a nanocrystalline vanadia with an amorphous V 2O 5 IGF separating the crystals. Thin (˜1 to a few nanometer thick) IGFs are known to be present in most polycrystalline oxide materials. However, the role of such a film on Li transport in oxide cathodes has not been addressed. Current scanning probe microscopy (SPM) studies have shown that the orientation of the layered nanocrystalline vanadia crystals near the cathode/solid electrolyte interface is not optimized for Li ion transport. While the precise structure of the material between the crystals has not been identified, initially it can be initially considered as likely to be a thin non-crystalline (amorphous) film. This is based on the ubiquitous presence of such a structure in other polycrystalline oxides. Also, and with more relevance to the materials used in thin film batteries, an amorphous film can be expected to form between nanocrystals that crystallized from an amorphous matrix, as would be the case in a deposited thin film cathode. Consistent with simulations of Li transport in amorphous vanadia, the current simulations show that Li ions diffuse more rapidly into the amorphous intergranular thin film than into the layered vanadia with the (0 0 1) planes parallel to the cathode/electrolyte interface.

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.

Amorphous InGaMgO Ultraviolet Photo-TFT with Ultrahigh Photosensitivity and Extremely Large Responsivity.

PubMed

Zhang, Yiyu; Qian, Ling-Xuan; Wu, Zehan; Liu, Xingzhao

2017-02-13

Recently, amorphous InGaZnO ultraviolet photo thin-film transistors have exhibited great potential for application in future display technologies. Nevertheless, the transmittance of amorphous InGaZnO (~80%) is still not high enough, resulting in the relatively large sacrifice of aperture ratio for each sensor pixel. In this work, the ultraviolet photo thin-film transistor based on amorphous InGaMgO, which processes a larger bandgap and higher transmission compared to amorphous InGaZnO, was proposed and investigated. Furthermore, the effects of post-deposition annealing in oxygen on both the material and ultraviolet detection characteristics of amorphous InGaMgO were also comprehensively studied. It was found that oxygen post-deposition annealing can effectively reduce oxygen vacancies, leading to an optimized device performance, including lower dark current, higher sensitivity, and larger responsivity. We attributed it to the combined effect of the reduction in donor states and recombination centers, both of which are related to oxygen vacancies. As a result, the 240-min annealed device exhibited the lowest dark current of 1.7 × 10 -10 A, the highest photosensitivity of 3.9 × 10⁶, and the largest responsivity of 1.5 × 10⁴ A/W. Therefore, our findings have revealed that amorphous InGaMgO photo thin-film transistors are a very promising alternative for UV detection, especially for application in touch-free interactive displays.

Effect of point defects on the amorphization of metallic alloys during ion implantation. [NiTi

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

Pedraza, D.F.; Mansur, L.K.

1985-01-01

A theoretical model of radiation-induced amorphization of ordered intermetallic compounds is developed. The mechanism is proposed to be the buildup of lattice defects to very high concentrations, which destabilizes the crystalline structure. Because simple point defects do not normally reach such levels during irradiation, a new defect complex containing a vacancy and an interstitial is hypothesized. Crucial properties of the complex are that the interstitial sees a local chemical environment similar to that of an atom in the ordered lattice, that the formation of the complex prevents mutual recombination and that the complex is immobile. The evolution of a disordermore » based on complexes is not accompanied by like point defect aggregation. The latter leads to the development of a sink microstructure in alloys that do not become amorphous. For electron irradiation, the complexes form by diffusional encounters. For ion irradiation, complexes are also formed directly in cascades. The possibility of direct amorphization in cascades is also included. Calculations for the compound NiTi show reasonable agreement with measured amorphization kinetics.« less

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.

Structural simplicity as a restraint on the structure of amorphous silicon

NASA Astrophysics Data System (ADS)

Cliffe, Matthew J.; Bartók, Albert P.; Kerber, Rachel N.; Grey, Clare P.; Csányi, Gábor; Goodwin, Andrew L.

2017-06-01

Understanding the structural origins of the properties of amorphous materials remains one of the most important challenges in structural science. In this study, we demonstrate that local "structural simplicity", embodied by the degree to which atomic environments within a material are similar to each other, is a powerful concept for rationalizing the structure of amorphous silicon (a -Si) a canonical amorphous material. We show, by restraining a reverse Monte Carlo refinement against pair distribution function (PDF) data to be simpler, that the simplest model consistent with the PDF is a continuous random network (CRN). A further effect of producing a simple model of a -Si is the generation of a (pseudo)gap in the electronic density of states, suggesting that structural homogeneity drives electronic homogeneity. That this method produces models of a -Si that approach the state-of-the-art without the need for chemically specific restraints (beyond the assumption of homogeneity) suggests that simplicity-based refinement approaches may allow experiment-driven structural modeling techniques to be developed for the wide variety of amorphous semiconductors with strong local order.

Influence of sample preparation on the transformation of low-density to high-density amorphous ice: An explanation based on the potential energy landscape

NASA Astrophysics Data System (ADS)

Giovambattista, Nicolas; Starr, Francis W.; Poole, Peter H.

2017-07-01

Experiments and computer simulations of the transformations of amorphous ices display different behaviors depending on sample preparation methods and on the rates of change of temperature and pressure to which samples are subjected. In addition to these factors, simulation results also depend strongly on the chosen water model. Using computer simulations of the ST2 water model, we study how the sharpness of the compression-induced transition from low-density amorphous ice (LDA) to high-density amorphous ice (HDA) is influenced by the preparation of LDA. By studying LDA samples prepared using widely different procedures, we find that the sharpness of the LDA-to-HDA transformation is correlated with the depth of the initial LDA sample in the potential energy landscape (PEL), as characterized by the inherent structure energy. Our results show that the complex phenomenology of the amorphous ices reported in experiments and computer simulations can be understood and predicted in a unified way from knowledge of the PEL of the system.

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

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.

Ternary graphene/amorphous carbon/nickel nanocomposite film for outstanding superhydrophobicity

NASA Astrophysics Data System (ADS)

Zhu, Xiaobo; Zhou, Shengguo; Yan, Qingqing

2018-04-01

A novel superhydrophobic ternary graphene/amorphous carbon/nickel (G-Ni/a-C:H) carbon-based film was fabricated by a green approach of high-voltage electrochemical deposition without using aqueous solution, which was systematically investigated including the structure and relating applications on self-cleaning and corrosion resistance. Graphene and nickel nano-particle inserts were effective to tailor the feature of nanocrystallite/amorphous microstructure as well as micro-nanoscale hierarchical rose-petal-like surface for G-Ni/a-C:H carbon-based film. Surprisingly, this deposit could present outstanding superhydrophobicity with the contact angle of 158.98 deg and sliding angle of 2.75 deg without any further surface modification meanwhile it could possess fairly well adhesion. Furthermore, the superhydrophobic G-Ni/a-C:H carbon-based film could exhibit excellent corrosion resistance and self-cleaning performances compared to no graphene incorporated deposit. The procedure of fabricating deposit might be simple, scalable, and environmental friendly, indicating a promising prospect for industrial applications in the field of anti-fouling, anti-corrosion and drag resistance.

Amorphous nickel incorporated tin oxide thin film transistors

NASA Astrophysics Data System (ADS)

Yang, Jianwen; Ren, Jinhua; Lin, Dong; Han, Yanbing; Qu, Mingyue; Pi, Shubin; Fu, Ruofan; Zhang, Qun

2017-09-01

Nickel as a dopant has been proposed to suppress excess carrier concentration in n-type tin oxide based thin film transistors (TFTs). The influences of Ni content on nickel doped tin oxide (TNO) thin films and their corresponding TFTs were investigated with experimental results showing that the TNO thin films are amorphous. Through the comparison of the transfer characteristic curves of the TNO TFTs with different Ni contents, it was observed that Ni doping is useful to improve the performance of SnO2-based TFTs by suppressing the off-state current and shifting the threshold voltage to 0 V. The amorphous TNO TFT with 3.3 at.% Ni content shows optimum performance, with field effect mobility of 8.4 cm2 V-1 s-1, saturation mobility of 6.8 cm2 V-1 s-1, subthreshold swing value of 0.8 V/decade, and an on-off current ratio of 2.1  ×  107. Nevertheless, the bias stress stability of SnO2-based TFTs deteriorate.

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.

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

Preservation of amorphous ultrafine material: A proposed proxy for slip during recent earthquakes on active faults

NASA Astrophysics Data System (ADS)

Hirono, Tetsuro; Asayama, Satoru; Kaneki, Shunya; Ito, Akihiro

2016-11-01

The criteria for designating an “Active Fault” not only are important for understanding regional tectonics, but also are a paramount issue for assessing the earthquake risk of faults that are near important structures such as nuclear power plants. Here we propose a proxy, based on the preservation of amorphous ultrafine particles, to assess fault activity within the last millennium. X-ray diffraction data and electron microscope observations of samples from an active fault demonstrated the preservation of large amounts of amorphous ultrafine particles in two slip zones that last ruptured in 1596 and 1999, respectively. A chemical kinetic evaluation of the dissolution process indicated that such particles could survive for centuries, which is consistent with the observations. Thus, preservation of amorphous ultrafine particles in a fault may be valuable for assessing the fault’s latest activity, aiding efforts to evaluate faults that may damage critical facilities in tectonically active zones.

Mechanical properties of graphene oxides.

PubMed

Liu, Lizhao; Zhang, Junfeng; Zhao, Jijun; Liu, Feng

2012-09-28

The mechanical properties, including the Young's modulus and intrinsic strength, of graphene oxides are investigated by first-principles computations. Structural models of both ordered and amorphous graphene oxides are considered and compared. For the ordered graphene oxides, the Young's modulus is found to vary from 380 to 470 GPa as the coverage of oxygen groups changes, respectively. The corresponding variations in the Young's modulus of the amorphous graphene oxides with comparable coverage are smaller at 290-430 GPa. Similarly, the ordered graphene oxides also possess higher intrinsic strength compared with the amorphous ones. As coverage increases, both the Young's modulus and intrinsic strength decrease monotonically due to the breaking of the sp(2) carbon network and lowering of the energetic stability for the ordered and amorphous graphene oxides. In addition, the band gap of the graphene oxide becomes narrower under uniaxial tensile strain, providing an efficient way to tune the electronic properties of graphene oxide-based materials.

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.

CO2-Assisted Conversion of Crystal Two-Dimensional Molybdenum Oxide to Amorphism with Plasmon Resonances.

PubMed

Liu, Wei; Xu, Qun

2018-04-20

Localized surface plasmon resonances (LSPRs) of ultra-thin two-dimensional (2D) nanomaterials opened a new regime in plasmonics in the last several years. 2D plasmonic materials are yet concentrated on the crystal structure, amorphous materials are hardly reported because of their limited preparation methods rather than undesired plasmonic properties. Taking molybdenum oxides as an example, herein, we elaborate the 2D amorphous plasmons prepared with the assistance of supercritical CO2. In brief, we examine the reported characteristic plasmonic properties of molybdenum oxides, and applications of supercritical CO2 in formations of 2D layer materials as well as introduced phase and disorder engineering based on our researchs. Furthermore, we propose our perspective on the development of 2D plasmons, especially for amorphous layer materials in the future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Channeling implantation of high energy carbon ions in a diamond crystal: Determination of the induced crystal amorphization

NASA Astrophysics Data System (ADS)

Erich, M.; Kokkoris, M.; Fazinić, S.; Petrović, S.

2018-02-01

This work reports on the induced diamond crystal amorphization by 4 MeV carbon ions implanted in the 〈1 0 0〉 oriented crystal and its determination by application of RBS/C and EBS/C techniques. The spectra from the implanted samples were recorded for 1.2, 1.5, 1.75 and 1.9 MeV protons. For the two latter ones the strong resonance of the nuclear elastic scattering 12C(p,p0)12C at 1.737 MeV was explored. The backscattering channeling spectra were successfully fitted and the ion beam induced crystal amorphization depth profile was determined using a phenomenological approach, which is based on the properly defined Gompertz type dechanneling functions for protons in the 〈1 0 0〉 diamond crystal channels and the introduction of the concept of ion beam amorphization, which is implemented through our newly developed computer code CSIM.

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.

Segal crystallinity index revisited by the simulation of x-ray diffraction patterns of cotton cellulose IB and cellulose II

USDA-ARS?s Scientific Manuscript database

The Segal method estimates the amorphous fraction of cellulose IB materials simply based on intensity at 18o 20 in an X-ray diffraction pattern and was extended to cellulose II using 16o 2O intensity. To address the dependency of Segal amorphous intensity on crystal size, cellulose polymorph, and th...

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.

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.

An investigation of passivity and breakdown of amorphous chromium-bromine thin films for surface modification of metallic biomaterials

NASA Astrophysics Data System (ADS)

Cormier, Lyne Mercedes

1998-12-01

The objectives of this investigation of amorphous Cr-B thin films as prospective coatings for biomaterials applications were to (i) produce and characterize an amorphous Cr-B thin film coating by magnetron sputtering, (ii) evaluate its corrosion resistance in physiologically relevant electrolytes, and (iii) propose a mechanism for the formation/dissolution of the passive film formed on amorphous Cr-B in chloride-containing near-neutral salt electrolytes. Dense (zone T) amorphous Cr75B25 thin films produced by DC magnetron sputtering were found to be better corrosion barriers than nanoczystalline or porous (zone 1) amorphous Cr75B25 thin films. The growth morphology and microstructure were a function of the sputtering pressure and substrate temperature, in agreement with the structure zone model of Thornton. The passivity/loss of passivity of amorphous Cr 75B25 in near-neutral salt solutions was explained using a modified bipolar layer model. The chromate ions identified by X-Ray Photoelectron Spectroscopy (XPS) in the outer layer of the passive film were found to play a determinant role in the passive behaviour of amorphous Cr75B 25 thin films in salt solutions. In near-neutral salt solutions of pH = 5 to 7, a decrease in pH combined with an increase in chloride concentration resulted in less dissolution of the Cr75B25 thin films. The apparent breakdown potential at 240 mV (SCE) obtained by Cyclic Potentiodynamic Anodic Polarization (CPAP) was associated with oxidation of species within the passive film, but not to dissolution leading to immediate loss of passivity. Pit Propagation Rate (PPR) testing evaluated the stable pitting potential to be between 600 and 650 mV. Amorphous Cr75B25 thin films ranked the best among other Cr-based materials such as 316L stainless steel, CrB2 and Cr investigated in this study for general corrosion behaviour in NaCl and Hanks solutions by CPAP testing. In terms of corrosion resistance, amorphous Cr75B25 thin films were recognized as a promising material for surface modification of biomaterials.

Quantitative HAADF STEM of SiGe in presence of amorphous surface layers from FIB preparation.

PubMed

Grieb, Tim; Tewes, Moritz; Schowalter, Marco; Müller-Caspary, Knut; Krause, Florian F; Mehrtens, Thorsten; Hartmann, Jean-Michel; Rosenauer, Andreas

2018-01-01

The chemical composition of four Si 1-x Ge x layers grown on silicon was determined from quantitative scanning transmission electron microscopy (STEM). The chemical analysis was performed by a comparison of the high-angle annular dark field (HAADF) intensity with multislice simulations. It could be shown that amorphous surface layers originating from the preparation process by focused-ion beam (FIB) at 30 kV have a strong influence on the quantification: the local specimen thickness is overestimated by approximately a factor of two, and the germanium concentration is substantially underestimated. By means of simulations, the effect of amorphous surface layers on the HAADF intensity of crystalline silicon and germanium is investigated. Based on these simulations, a method is developed to analyze the experimental HAADF-STEM images by taking the influence of the amorphous layers into account which is done by a reduction of the intensities by multiplication with a constant factor. This suggested modified HAADF analysis gives germanium concentrations which are in agreement with the nominal values. The same TEM lamella was treated with low-voltage ion milling which removed the amorphous surface layers completely. The results from subsequent quantitative HAADF analyses are in agreement with the nominal concentrations which validates the applicability of the used frozen-lattice based multislice simulations to describe the HAADF scattering of Si 1-x Ge x in STEM. Copyright © 2017 Elsevier B.V. All rights reserved.

Third-order nonlinear optical properties of soluble Cr(III)-dioxolene complexes

NASA Astrophysics Data System (ADS)

Noro, Shin-ichiro; Sassa, Takafumi; Aoyama, Tetsuya; Chang, Ho-Chol; Kitagawa, Susumu; Wada, Tatsuo

2004-10-01

We synthesized novel ligand-based mixed valence (LBMV) CrIII-dioxolene complexes, [Cr(X4SQ)(X4Cat)(4,4'-di-tert-butyl-2,2'-bpy)] (SQ = semiquinone, Cat = catecohol, 2,2'-bpy = 2,2'-bipyridine; X = Cl (2a) and Br (2b)) and [Cr(X4SQ)(X4Cat)(4,4'-dinonyl-2,2'-bpy)] (X = Cl (3a) and Br (3b)), and prepared thin films for investigating their third-order nonlinear optical (NLO) properties in terms of the mixed valence states. Electronic absorption spectra of these complexes in solution and solid states showed an intervalence charge-transfer (IVCT) band from Cat2- to SQ"- at the IR region, indicating of a coexistence of SQ and Cat ligands, namely, LBMV state of the complexes. These complexes were well soluble in nonpolar organic solvent, which allowed us to prepare thin films by spin coating. The obtained films showed the electronic absorption spectra similar to those in solution and were amorphous because of steric hindrance of halogen and alkyl substituents in o-dioxolene and 2,2'-bpy moieties, respectively. The x(3) values of the films of 3a and 3b with a thickness of 30 ~ 40 nm were determined for 1.0 × 10-12 esu at 1.907 μm.

Micro- and Nanostructures of SAFOD Core Samples - First Results

NASA Astrophysics Data System (ADS)

Janssen, C.; Wirth, R.; Rybacki, E.; Naumann, R.; Kemnitz, H.; Wenk, H.; Dresen, G. H.

2009-12-01

Microstructures and chemical composition of ultra-cataclastic rocks from the San Andreas Fault drill hole (SAFOD) were examined using TEM, SEM and XRD analyses. The ultra-cataclasites are mainly composed of quartz, clay minerals (illite/smectite, chlorite), feldspar (plagioclase) and calcite with grain sizes between 200 nm and 500 μm. In particular we found: (1) amorphous materials, identified by transmission electron microscopy. Chemical analyses suggest that all amorphous material was formed by comminution (crush-origin) of fragments rather than by melting (melt-origin) and that the observed amorphous phases may act as hydrodynamic lubricating layers that reduce friction in the San Andreas Fault. (2) Pressure solution seams and localized precipitation of hydrous mixed-layered clay minerals suggest intensive dissolution-precipitation processes. These may lead to a thin film covering slip surfaces. (3) Authigenic clay minerals forming a flocculated fabric. (4) The fine-grained (< 1μm) gouge matrix contains clasts (feldspar, quartz) and is frequently cut by fault-related veins. The veins are filled with calcite or quartz. Observed micorstructures in the fine-grained matrix suggest comminution and sliding of the nanoscale grains. Open pore spaces up to 2.25 μm3 have been formed during and after deformation within the gouge matrix. These were possibly filled with hydrothermal fluids at elevated pore fluid pressure preventing closure. (5) Detrital quartz and feldspar grains are partly dissolved and replaced by authigenic illite-smectite (I-S) mixed-layer clay minerals. TEM imaging of these grains reveal that initial alteration processes started within pores and small fissures of grains. The crystallographic-preferred orientation of illite and I/S grains is rather weak with a maximum m.r.d. (multiples of random orientation) of 2.3. (6) Some older fault-related vein-calcites show evidence for intense intracrystalline plasticity (deformation twins and dislocation creep). Dislocation densities in calcite grains indicate a local maximum stress of about 40 MPa. The younger fault-related vein-calcite generation with elongated to fibrous habit suggests slow opening by aseismic slip. These crystals are not fractured or twinned (or only less); indicating that healing processes (cementation) outlasted deformation.

Label-Free Direct Electronic Detection of Biomolecules with Amorphous Silicon Nanostructures

PubMed Central

Lund, John; Mehta, Ranjana; Parviz, Babak A.

2007-01-01

We present the fabrication and characterization of a nano-scale sensor made of amorphous silicon for the label-free, electronic detection of three classes of biologically important molecules: ions, oligonucleotides, and proteins. The sensor structure has an active element which is a 50 nm wide amorphous silicon semicircle and has a total footprint of less than 4 μm2. We demonstrate the functionalization of the sensor with receptor molecules and the electronic detection of three targets: H+ ions, short single-stranded DNAs, and streptavidin. The sensor is able to reliably distinguish single base-pair mismatches in 12 base long strands of DNA and monitor the introduction and identification of straptavidin in real-time. The versatile sensor structure can be readily functionalized with a wide range of receptor molecules and is suitable for integration with high-speed electronic circuits as a post-process on an integrated circuit chip. PMID:17292148

Variations in contrast of scanning electron microscope images for microstructure analysis of Si-based semiconductor materials.

PubMed

Itakura, Masaru; Kuwano, Noriyuki; Sato, Kaoru; Tachibana, Shigeaki

2010-08-01

Image contrasts of Si-based semiconducting materials have been investigated by using the latest scanning electron microscope with various detectors under a range of experimental conditions. Under a very low accelerating voltage (500 V), we obtained a good image contrast between crystalline SiGe whiskers and the amorphous matrix using an in-lens secondary electron (SE) detector, while the conventional topographic SE image and the compositional backscattered electron (BSE) image gave no distinct contrast. By using an angular-selective BSE (AsB) detector for wide-angle scattered BSE, on the other hand, the crystal grains in amorphous matrix can be clearly visualized as 'channelling contrast'. The image contrast is very similar to that of their transmission electron microscope image. The in-lens SE (true SE falling dots SE1) and the AsB (channelling) contrasts are quite useful to distinguish crystalline parts from amorphous ones.

(Zr,Ti)O2 interface structure in ZrO2-TiO2 nanolaminates with ultrathin periodicity

NASA Astrophysics Data System (ADS)

Aita, C. R.; DeLoach, J. D.; Yakovlev, V. V.

2002-07-01

A mixed cation interfacial structure in ZrO2-TiO2 nanolaminate films with ultrathin bilayer periodicity grown by sputter deposition at 297 K was identified by x-ray diffraction and nonresonant Raman spectroscopy. This structure consists of an amorphous phase at a ZrO2-on-TiO2 bilayer interface, followed by an extensive crystalline monoclinic (Zr,Ti)O2 solid solution predicted by Vegard's law. Monoclinic (Zr,Ti)O2 has previously been reported only once, in bulk powder of a single composition (ZrTiO4) at high pressure. Its stabilization in the nanolaminates is explained by the Gibbs-Thomson effect. This complex interfacial structure is shown to be a means of accommodating chemical mixing in the absence of a driving force for heteroepitaxy.

Synthesis of FeCoB amorphous nanoparticles and application in ferrofluids

NASA Astrophysics Data System (ADS)

Zhao, Shuchun; Bian, Xiufang; Yang, Chuncheng; Yu, Mengchun; Wang, Tianqi

2018-03-01

Magnetic FeCoB amorphous nanoparticles were successfully synthesized by borohydride reduction in water/n-hexane (W/He) microemulsions. The as-prepared FeCoB alloys are amorphous and spherical nanoparticles with an average particle size about 10.7 nm, compared to FeCoB alloys with an average particle size about 304.2 nm which were synthesized by a conventional aqua-solution method. Furthermore, three kinds of FeCoB ferrofluids (FFs) were prepared by dispersing FeCoB particles into W/He microemulsion, water and silicone oil respectively. Results show that the W/He-based FeCoB FFs are superparamagnetic with saturation magnetization (Ms) reaching to 12.4 emu/g. Besides, compared to water-based and silicone oil-based FFs, W/He-based FeCoB FFs exhibit high stability, with magnetic weights decreasing slightly even under the magnetic field intensity of H = 210 mT. In the W/He-based FeCoB FFs, interfacial tensions of water phase and oil phase are supposed to prevent the agglomeration and sedimentation of FeCoB nanoparticles dispersed in different water droplets of the microemulsion, compared to the current stabilizing method of directly modifying the surface of particles.

Formation of Ti-Ta-based surface alloy on TiNi SMA substrate from thin films by pulsed electron-beam melting

NASA Astrophysics Data System (ADS)

Meisner, L. L.; Markov, A. B.; Ozur, G. E.; Rotshtein, V. P.; Yakovlev, E. V.; Meisner, S. N.; Poletika, T. M.; Girsova, S. L.; Semin, V. O.; Mironov, Yu P.

2017-05-01

TiNi shape memory alloys (SMAs) are unique metallic biomaterials due to combination of superelastisity and high corrosion resistance. Important factors limiting biomedical applications of TiNi SMAs are a danger of toxic Ni release into the adjacent tissues, as well as insufficient level of X-ray visibility. In this paper, the method for fabrication of protective Ni-free surface alloy of thickness ∼1 μm of near Ti70Ta30 composition on TiNi SMA substrate has been successfully realized. The method is based on multiple alternation of magnetron co-deposition of Ti70Ta30 thin (50 nm) films and their liquid-phase mixing with the TiNi substrate by microsecond low-energy, high current electron beam (≤15 keV, ∼2 J/cm2) using setup RITM-SP (Microsplav, Russia). It was found by AES, XRD, SEM/EDS and HRTEM/EDS examinations, that Ti-Ta surface alloy has an increased X-ray visibility and gradient multiphase amorphous-nanocrystalline structure containing nanopores.

Infrared and Raman spectroscopic studies on alkali borate glasses: evidence of mixed alkali effect.

PubMed

Padmaja, G; Kistaiah, P

2009-03-19

A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition.

Diagenesis of the Oligocene-Miocene rocks of the Upper Floridan and Intermediate aquifer systems by meteoric and mixing-zone waters in southwest Florida

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

Weedman, S.D.; McCartan, L.

1993-03-01

Optical and SEM of samples from 6 cores of Oligocene and Miocene rocks that compose portions of the Florida and Intermediate aquifers and the intervening semiconfining unit documents meteoric and mixing-zone (seawater and fresh carbonate ground water) diagenesis inferred to have occurred over several cycles of sea level change. Dolomite, limestone, sandstone, and claystone of the Suwannee Formation and the Arcadia Formation (Hawthorn Group) were examined. Core samples from time-equivalent strata in two E--W transects in Manatee, Hardee, Highlands, Sarasota, and DeSoto Counties are estimated to be 16--33 Ma on the basis of [sup 87]Sr/[sup 86]Sr ratios from unaltered molluskmore » shells and by molluscan biostratigraphy. Lithostratigraphic correlations are based on examination of 19 cores, 62 thin sections, 60 geophysical logs, and mineralogy determined by X-ray diffraction. Diagenetic indicators that the authors tracked petrographically include shell micritization, shell dissolution, equant and (or) fibrous CaCO[sub 3] cement, neomorphism, dolomite, etched phosphate grains, echinoderm fragment syntaxial overgrowths, and amorphous silica pore lining. Infiltration of meteoric water caused dissolution of carbonate minerals, especially aragonite, and precipitation of equant calcite crystals in voids of dissolved fossils and in pore spaces between grains. The silica was precipitated as pore linings in zones having soil textures. Observed replacement of calcite by limpid dolomite is consistent with modeling predictions of mixing-zone diagenesis. Etched crystals of limpid dolomite may indicate freshwater dissolution of a mixing-zone precipitate. Mapping of regional unconformities revealed pronounced thickening and thinning of some units. Evidence of meteoric water diagenesis is observed in the upper 600 ft of the transects examined. Evidence of mixing-zone diagenesis is observed at varying depths, but appears to increase in abundance and thickness toward the west.« less

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.

Recoil-free Fraction in Amorphous and Nanocrystalline Aluminium Based Alloys

NASA Astrophysics Data System (ADS)

Sitek, Jozef

2008-10-01

Aluminium based rapidly quenched alloys of nominal composition Al90Fe7Nb3 and Al94Fe2V4 were studied by Mössbauer spectroscopy. We have measured the recoil-free fraction and thermal shift at room and liquid nitrogen temperature. The frequency modes of atomic vibrations were determined and consequently the characteristic Debye temperature was derived. Characteristic temperature calculated from f-factor was lower than those fitted from second order Doppler shift. This indicates the presence of different frequency modes for amorphous and nanocrystalline states.

Omni-directional selective shielding material based on amorphous glass coated microwires.

PubMed

Ababei, G; Chiriac, H; David, V; Dafinescu, V; Nica, I

2012-01-01

The shielding effectiveness of the omni-directional selective shielding material based on CoFe-glass coated amorphous wires in 0.8 GHz-3 GHz microwave frequency range is investigated. The measurements were done in a controlled medium using a TEM cell and in the free space using horn antennas, respectively. Experimental results indicate that the composite shielding material can be developed with desired shielding effectiveness and selective absorption of the microwave frequency range by controlling the number of the layers and the length of microwires.

Enhanced performance of a structured cyclo olefin copolymer-based amorphous silicon solar cell

NASA Astrophysics Data System (ADS)

Zhan, Xinghua; Chen, Fei; Gao, Mengyu; Tie, Shengnian; Gao, Wei

2017-07-01

The submicron array was fabricated onto a cyclo olefin copolymer (COC) film by a hot embossing method. An amorphous silicon p-i-n junction and transparent conductive layers were then deposited onto it through a plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering. The efficiency of the fabricated COC-based solar cell was measured and the result demonstrated 18.6% increase of the solar cell efficiency when compared to the sample without array structure. The imprinted polymer solar cells with submicron array indeed increase their efficiency.

High Infrared Blocking Cellulose Film Based on Amorphous to Anatase Transition of TiO2 via Atomic Layer Deposition.

PubMed

Li, Wenbin; Li, Linfeng; Wu, Xi; Li, Junyu; Jiang, Lang; Yang, Hongjun; Ke, Guizhen; Cao, Genyang; Deng, Bo; Xu, Weilin

2018-06-27

A high IR-blocking cellulose film was designed based on an amorphous to anatase transition of TiO 2 using atomic layer deposition (ALD). This transition was realized at 250 °C, at which the cellulose is thermal stable. Optimized ALD condition of 250 °C and 1200 cycles give us an excellent heat insulator, which could significantly reduce the enclosed space temperature from 59.2 to 51.9 °C after exposure to IR lamp for 5 min.

A method for generating reliable atomistic models of amorphous polymers based on a random search of energy minima

NASA Astrophysics Data System (ADS)

Curcó, David; Casanovas, Jordi; Roca, Marc; Alemán, Carlos

2005-07-01

A method for generating atomistic models of dense amorphous polymers is presented. The method is organized in a two-steps procedure. First, structures are generated using an algorithm that minimizes the torsional strain. After this, a relaxation algorithm is applied to minimize the non-bonding interactions. Two alternative relaxation methods, which are based simple minimization and Concerted Rotation techniques, have been implemented. The performance of the method has been checked by simulating polyethylene, polypropylene, nylon 6, poly(L,D-lactic acid) and polyglycolic acid.

Nanoscale Control over the Mixing Behavior of Surface-Confined Bicomponent Supramolecular Networks Using an Oriented External Electric Field

PubMed Central

2017-01-01

Strong electric fields are known to influence the properties of molecules as well as materials. Here we show that by changing the orientation of an externally applied electric field, one can locally control the mixing behavior of two molecules physisorbed on a solid surface. Whether the starting two-component network evolves into an ordered two-dimensional (2D) cocrystal, yields an amorphous network where the two components phase separate, or shows preferential adsorption of only one component depends on the solution stoichiometry. The experiments are carried out by changing the orientation of the strong electric field that exists between the tip of a scanning tunneling microscope and a solid substrate. The structure of the two-component network typically changes from open porous at negative substrate bias to relatively compact when the polarity of the applied bias is reversed. The electric-field-induced mixing behavior is reversible, and the supramolecular system exhibits excellent stability and good response efficiency. When molecular guests are adsorbed in the porous networks, the field-induced switching behavior was found to be completely different. Plausible reasons behind the field-induced mixing behavior are discussed. PMID:29112378

Thin film solar cells with Si nanocrystallites embedded in amorphous intrinsic layers by hot-wire chemical vapor deposition.

PubMed

Park, Seungil; Parida, Bhaskar; Kim, Keunjoo

2013-05-01

We investigated the thin film growths of hydrogenated silicon by hot-wire chemical vapor deposition with different flow rates of SiH4 and H2 mixture ambient and fabricated thin film solar cells by implementing the intrinsic layers to SiC/Si heterojunction p-i-n structures. The film samples showed the different infrared absorption spectra of 2,000 and 2,100 cm(-1), which are corresponding to the chemical bonds of SiH and SiH2, respectively. The a-Si:H sample with the relatively high silane concentration provides the absorption peak of SiH bond, but the microc-Si:H sample with the relatively low silane concentration provides the absorption peak of SiH2 bond as well as SiH bond. Furthermore, the microc-Si:H sample showed the Raman spectral shift of 520 cm(-1) for crystalline phase Si bonds as well as the 480 cm(-1) for the amorphous phase Si bonds. These bonding structures are very consistent with the further analysis of the long-wavelength photoconduction tail and the formation of nanocrystalline Si structures. The microc-Si:H thin film solar cell has the photovoltaic behavior of open circuit voltage similar to crystalline silicon thin film solar cell, indicating that microc-Si:H thin film with the mixed phase of amorphous and nanocrystalline structures show the carrier transportation through the channel of nanocrystallites.

Microfibrous Solid Dispersions of Poorly Water-Soluble Drugs Produced via Centrifugal Spinning: Unexpected Dissolution Behavior on Recrystallization.

PubMed

Marano, Stefania; Barker, Susan A; Raimi-Abraham, Bahijja T; Missaghi, Shahrzad; Rajabi-Siahboomi, Ali; Aliev, Abil E; Craig, Duncan Q M

2017-05-01

Temperature-controlled, solvent-free centrifugal spinning may be used as a means of rapid production of amorphous solid dispersions in the form of drug-loaded sucrose microfibers. However, due to the high content of amorphous sucrose in the formulations, such microfibers may be highly hygroscopic and unstable on storage. In this study, we explore both the effects of water uptake of the microfibers and the consequences of deliberate recrystallization for the associated dissolution profiles. The stability of sucrose microfibers loaded with three selected BCS class II model drugs (itraconazole (ITZ), olanzapine (OLZ), and piroxicam (PRX)) was investigated under four different relative humidity conditions (11, 33, 53, and 75% RH) at 25 °C for 8 months, particularly focusing on the effect of the highest level of moisture (75% RH) on the morphology, size, drug distribution, physical state, and dissolution performance of microfibers. While all samples were stable at 11% RH, at 33% RH the ITZ-sucrose system showed greater resistance against devitrification compared to the OLZ- and PRX-sucrose systems. For all three samples, the freshly prepared microfibers showed enhanced dissolution and supersaturation compared to the drug alone and physical mixes; surprisingly, the dissolution advantage was largely maintained or even enhanced (in the case of ITZ) following the moisture-induced recrystallization under 75% RH. Therefore, this study suggests that the moisture-induced recrystallization process may result in considerable dissolution enhancement compared to the drug alone, while overcoming the physical stability risks associated with the amorphous state.

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.

R&D issues in scale-up and manufacturing of amorphous silicon tandem modules

NASA Astrophysics Data System (ADS)

Arya, R. R.; Carlson, D. E.; Chen, L. F.; Ganguly, G.; He, M.; Lin, G.; Middya, R.; Wood, G.; Newton, J.; Bennett, M.; Jackson, F.; Willing, F.

1999-03-01

R & D on amorphous silicon based tandem junction devices has improved the throughtput, the material utilization, and the performance of devices on commercial tin oxide coated glass. The tandem junction technology has been scaled-up to produce 8.6 Ft2 monolithically integrated modules in manufacturing at the TF1 plant. Optimization of performance and stability of these modules is ongoing.

Metallic glass coating on metals plate by adjusted explosive welding technique

NASA Astrophysics Data System (ADS)

Liu, W. D.; Liu, K. X.; Chen, Q. Y.; Wang, J. T.; Yan, H. H.; Li, X. J.

2009-09-01

Using an adjusted explosive welding technique, an aluminum plate has been coated by a Fe-based metallic glass foil in this work. Scanning electronic micrographs reveal a defect-free metallurgical bonding between the Fe-based metallic glass foil and the aluminum plate. Experimental evidence indicates that the Fe-based metallic glass foil almost retains its amorphous state and mechanical properties after the explosive welding process. Additionally, the detailed explosive welding process has been simulated by a self-developed hydro-code and the bonding mechanism has been investigated by numerical analysis. The successful welding between the Fe-based metallic glass foil and the aluminum plate provides a new way to obtain amorphous coating on general metal substrates.

pH control of the structure, composition, and catalytic activity of sulfated zirconia

NASA Astrophysics Data System (ADS)

Ivanov, Vladimir K.; Baranchikov, Alexander Ye.; Kopitsa, Gennady P.; Lermontov, Sergey A.; Yurkova, Lyudmila L.; Gubanova, Nadezhda N.; Ivanova, Olga S.; Lermontov, Anatoly S.; Rumyantseva, Marina N.; Vasilyeva, Larisa P.; Sharp, Melissa; Pranzas, P. Klaus; Tretyakov, Yuri D.

2013-02-01

We report a detailed study of structural and chemical transformations of amorphous hydrous zirconia into sulfated zirconia-based superacid catalysts. Precipitation pH is shown to be the key factor governing structure, composition and properties of amorphous sulfated zirconia gels and nanocrystalline sulfated zirconia. Increase in precipitation pH leads to substantial increase of surface fractal dimension (up to ˜2.7) of amorphous sulfated zirconia gels, and consequently to increase in specific surface area (up to ˜80 m2/g) and simultaneously to decrease in sulfate content and total acidity of zirconia catalysts. Complete conversion of hexene-1 over as synthesized sulfated zirconia catalysts was observed even under ambient conditions.

Localization and stability in damageable amorphous solids

NASA Astrophysics Data System (ADS)

de Tommasi, D.; Marzano, S.; Puglisi, G.; Saccomandi, G.

2010-01-01

In the present article, based on a recently proposed model (De Tommasi et al. in J Rheol 50:495-512, 2006; Phys Rev Lett 100:085502, 2008), we analyze the influence of the microstructure properties on the damage behavior of amorphous materials. In accordance with the experimental observations, different scenarios of damage nucleation and evolution are associated to different material distributions at the microscale. In particular, we observe the possibilities of uniform or localized damage and strain geometries with a macroscopic behavior that may range from brittle to ductile or rubber-like. To describe the possibility of extending our stability analysis to three-dimensional damageable amorphous bodies we consider a simple boundary value problem of engineering interest.

Microstructural properties and evolution of nanoclusters in liquid Si during a rapid cooling process

NASA Astrophysics Data System (ADS)

Gao, T.; Hu, X.; Li, Y.; Tian, Z.; Xie, Q.; Chen, Q.; Liang, Y.; Luo, X.; Ren, L.; Luo, J.

2017-11-01

The formation of amorphous structures in Si during the rapid quenching process was studied based on molecular dynamics simulation by using the Stillinger-Weber potential. The evolution characteristics of nanoclusters during the solidification were analyzed by several structural analysis methods. The amorphous Si has been formed with many tetrahedral clusters and few nanoclusters. During the solidification, tetrahedral polyhedrons affect the local structures by their different positions and connection modes. The main kinds of polyhedrons randomly linked with one another to form an amorphous network structures in the system. The structural evolution of crystal nanocluster demonstrates that the nanocluster has difficulty to growth because of the high cooling rate of 1012 K/s.

Thermally activated diffusion of copper into amorphous carbon

DOE PAGES

Appy, David; Wallingford, Mark; Jing, Dapeng; ...

2017-07-11

Using x-ray photoelectron spectroscopy, the authors characterize the thermally activated changes that occur when Cu is deposited on amorphous carbon supported on Si at 300 K, then heated to 800 K. The authors compare data for Cu on the basal plane of graphite with pinning defects, where scanning tunneling microscopy reveals that coarsening is the main process in this temperature range. Coarsening begins at 500–600 K and causes moderate attenuation of the Cu photoelectron signal. For Cu on amorphous carbon, heating to 800 K causes Cu to diffuse into the bulk of the film, based on the strong attenuation ofmore » the Cu signal. Diffusion into the bulk of the amorphous carbon film is confirmed by changes in the shape of the Cu 2 p inelastic tail, and by comparison of attenuation between Cu 2 p and Cu 3 p lines. The magnitude of the photoelectron signal attenuation is compatible with Cu distributed homogeneously throughout the amorphous carbon film, and is not compatible with Cu at or below the C–Si interface under the conditions of our experiments. As a result, desorption is not significant at temperatures up to 800 K.« 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.

DOE-DARPA High-Performance Corrosion-Resistant Materials (HPCRM), Annual HPCRM Team Meeting & Technical Review

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

Farmer, J; Brown, B; Bayles, B

The overall goal is to develop high-performance corrosion-resistant iron-based amorphous-metal coatings for prolonged trouble-free use in very aggressive environments: seawater & hot geothermal brines. The specific technical objectives are: (1) Synthesize Fe-based amorphous-metal coating with corrosion resistance comparable/superior to Ni-based Alloy C-22; (2) Establish processing parameter windows for applying and controlling coating attributes (porosity, density, bonding); (3) Assess possible cost savings through substitution of Fe-based material for more expensive Ni-based Alloy C-22; (4) Demonstrate practical fabrication processes; (5) Produce quality materials and data with complete traceability for nuclear applications; and (6) Develop, validate and calibrate computational models to enable lifemore » prediction and process design.« less

Synthesis, characterization and optical properties of non-traditional tellurite-selenite glasses

NASA Astrophysics Data System (ADS)

Bachvarova-Nedelcheva, A.; Iordanova, R.; Kostov, K. L.; Ganev, V.; Yordanov, St.

2014-06-01

This study continues our investigations on non-traditional tellurite-selenite amorphous materials. Two glasses containing TeO2, SeO2, MoO3 and V2O5 were obtained at high oxygen pressure (P = 36 MPa) using pure oxides as precursors. The real bulk chemical composition of both glasses was verified by LA-ICP-MS method. The glasses were characterized by X-ray diffraction, Scanning Electron Microscopy (SEM), Differential Thermal Analysis (DTA), UV-Vis, XPS, IR and EPR spectroscopy. According to DTA the glass transition temperature (Tg) is below 300 °C. Both glasses were subjected to heat treatment (300 °C - 12 h) and as a result no crystallization was observed. The main building units (TeO3, TeO4, Mo2O8, and SеО3) were determined by IR and X-ray photoelectron spectroscopy and the existence of mixed bridging bonds only, which build up the amorphous network. It was established by UV-Vis that the obtained glasses are transparent above 550 nm and they were red colored.

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

Structure of Hydrated Poly(d,l-lactic acid) Studied with X-ray Diffraction and Molecular Simulation Methods

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

Li, Xianfeng; Murthy, N. Sanjeeva; Latour, Robert A.

2012-10-10

The effect of hydration on the molecular structure of amorphous poly(D,L-lactic acid) (PDLLA) with 50:50 L-to-D ratio has been studied by combining experiments with molecular simulations. X-ray diffraction measurements revealed significant changes upon hydration in the structure functions of the copolymer. Large changes in the structure functions at 10 days of incubation coincided with the large increase in the water uptake from {approx} 1 to {approx} 40% and the formation of voids in the film. Computer modeling based on the recently developed TIGER2/TIGER3 mixed sampling scheme was used to interpret these changes by efficiently equilibrating both dry and hydrated modelsmore » of PDLLA. Realistic models of bulk amorphous PDLLA structure were generated as demonstrated by close agreement between the calculated and the experimental structure functions. These molecular simulations were used to identify the interactions between water and the polymer at the atomic level including the change of positional order between atoms in the polymer due to hydration. Changes in the partial O-O structure functions, about 95% of which were due to water-polymer interactions, were apparent in the radial distribution functions. These changes, and somewhat smaller changes in the C-C and C-O partial structure functions, clearly demonstrated the ability of the model to capture the hydrogen-bonding interactions between water and the polymer, with the probability of water forming hydrogen bonds with the carbonyl oxygen of the ester group being about 4 times higher than with its ether oxygen.« less

Structural changes in precipitates and cell model for the conversion of amorphous calcium phosphate to hydroxyapatite during the initial stage of precipitation

NASA Astrophysics Data System (ADS)

Zyman, Z.; Rokhmistrov, D.; Glushko, V.

2012-08-01

A new insight on the conversion of an amorphous calcium phosphate, ACP, to hydroxyapatite, HA, has been proposed. The ACP has been precipitated under appropriate conditions of the nitrous method (low concentrations of reactants, pH>10, 25 °С, fast mixing). The ACP to HA conversion has been found to commence immediately after the ACP precipitation. The conversion reveals itself in the first detected shift of the diffuse maximum from 29.5° 2θ (ACP) to about 32° 2θ (the position of principal peaks of HA) in the XRD patterns for the precipitates of 2 min-6 h lifetimes. The precipitates are biphasic mixtures of ACP and nanocrystalline HA, nHA, with increasing nHA/ACP ratio for longer lifetimes. Characteristics of the simulated XRD profiles calculated proceeding on such a picture are excellently confirmed by experimental results. At the end of the conversion, HA nanocrystals start growing. This follows from the appearance of broadened diffraction maxima, which gradually sharpen, along with the appearance and gradual increase of splitting of the initially featureless υ3 and υ4PO43- bands in the IR spectra of precipitates with their aging (after 6 h of the precipitation). Based on the detected structural and compositional peculiarities of ACP in the early stage of precipitation, a cell model for the HA crystallization has been proposed. Proceeding on the model, the principal data in this and earlier studies, considering the ACP to HA conversion as an internal rearrangement process in the ACP particles, has been reasonably explained.

Silicate Phases on the Surfaces of Trojan Asteroids

NASA Astrophysics Data System (ADS)

Martin, Audrey; Emery, Joshua P.; Lindsay, Sean S.

2017-10-01

Determining the origin of asteroids provides an effective means of constraining the solar system’s dynamic past. Jupiter Trojan asteroids (hereafter Trojans) may help in determining the amount of radial mixing that occurred during giant planet migration. Previous studies aimed at characterizing surface composition show that Trojans have low albedo surfaces and are spectrally featureless in the near infrared. The thermal infrared (TIR) wavelength range has advantages for detecting silicates on low albedo asteroids such as Trojans. The 10 μm region exhibits strong features due to the Si-O fundamental molecular vibrations. Silicates that formed in the inner solar system likely underwent thermal annealing, and thus are crystalline, whereas silicates that accreted in the outer solar system experienced less thermal processing, and therefore are more likely to have remained in an amorphous phase. We hypothesize that the Trojans formed in the outer solar system (i.e., the Kuiper Belt), and therefore will have a more dominant amorphous spectral silicate component. With TIR spectra from the Spitzer Space Telescope, we identify mineralogical features from the surface of 11 Trojan asteroids. Fine-grain mixtures of crystalline pyroxene and olivine exhibit a 10 μm feature with sharp cutoffs between about 9 μm and 12 μm, which create a broad flat plateau. Amorphous phases, when present, smooth the sharp emission features, resulting in a dome-like shape. Preliminary results indicate that the surfaces of analyzed Trojans contain primarily amorphous silicates. Emissivity spectra of asteroids 1986 WD and 4709 Ennomos include small peaks in the 10 μm region, diagnostic of small amounts of crystalline olivine. One explanation is that Trojans formed in the same region as Kuiper Belt objects, and when giant planet migration ensued, they were swept into Jupiter’s stable Lagrange points where they are found today. As such, it is possible that an ancestral group of Kuiper Belt objects were separated from Trojans during large planet migration.

Chiral nematic porous germania and germanium/carbon films

NASA Astrophysics Data System (ADS)

Xu, Jing; Nguyen, Thanh-Dinh; Xie, Kai; Hamad, Wadood Y.; MacLachlan, Mark J.

2015-07-01

We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering.We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering. Electronic supplementary information (ESI) available: TGA, IR, Raman, TEM, SEM, BET. See DOI: 10.1039/c5nr02520f

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-01-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (Tg) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and Tg curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-03-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (T g ) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and T g curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

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

Thin-film reliability and engineering overview

NASA Technical Reports Server (NTRS)

Ross, R. G., Jr.

1984-01-01

The reliability and engineering technology base required for thin film solar energy conversions modules is discussed. The emphasis is on the integration of amorphous silicon cells into power modules. The effort is being coordinated with SERI's thin film cell research activities as part of DOE's Amorphous Silicon Program. Program concentration is on temperature humidity reliability research, glass breaking strength research, point defect system analysis, hot spot heating assessment, and electrical measurements technology.

Thin-film reliability and engineering overview

NASA Astrophysics Data System (ADS)

Ross, R. G., Jr.

1984-10-01

The reliability and engineering technology base required for thin film solar energy conversions modules is discussed. The emphasis is on the integration of amorphous silicon cells into power modules. The effort is being coordinated with SERI's thin film cell research activities as part of DOE's Amorphous Silicon Program. Program concentration is on temperature humidity reliability research, glass breaking strength research, point defect system analysis, hot spot heating assessment, and electrical measurements technology.

Direct Growth of III-Nitride Nanowire-Based Yellow Light-Emitting Diode on Amorphous Quartz Using Thin Ti Interlayer

NASA Astrophysics Data System (ADS)

Prabaswara, Aditya; Min, Jung-Wook; Zhao, Chao; Janjua, Bilal; Zhang, Daliang; Albadri, Abdulrahman M.; Alyamani, Ahmed Y.; Ng, Tien Khee; Ooi, Boon S.

2018-02-01

Consumer electronics have increasingly relied on ultra-thin glass screen due to its transparency, scalability, and cost. In particular, display technology relies on integrating light-emitting diodes with display panel as a source for backlighting. In this study, we undertook the challenge of integrating light emitters onto amorphous quartz by demonstrating the direct growth and fabrication of a III-nitride nanowire-based light-emitting diode. The proof-of-concept device exhibits a low turn-on voltage of 2.6 V, on an amorphous quartz substrate. We achieved 40% transparency across the visible wavelength while maintaining electrical conductivity by employing a TiN/Ti interlayer on quartz as a translucent conducting layer. The nanowire-on-quartz LED emits a broad linewidth spectrum of light centered at true yellow color ( 590 nm), an important wavelength bridging the green-gap in solid-state lighting technology, with significantly less strain and dislocations compared to conventional planar quantum well nitride structures. Our endeavor highlighted the feasibility of fabricating III-nitride optoelectronic device on a scalable amorphous substrate through facile growth and fabrication steps. For practical demonstration, we demonstrated tunable correlated color temperature white light, leveraging on the broadly tunable nanowire spectral characteristics across red-amber-yellow color regime.

Direct Growth of III-Nitride Nanowire-Based Yellow Light-Emitting Diode on Amorphous Quartz Using Thin Ti Interlayer.

PubMed

Prabaswara, Aditya; Min, Jung-Wook; Zhao, Chao; Janjua, Bilal; Zhang, Daliang; Albadri, Abdulrahman M; Alyamani, Ahmed Y; Ng, Tien Khee; Ooi, Boon S

2018-02-06

Consumer electronics have increasingly relied on ultra-thin glass screen due to its transparency, scalability, and cost. In particular, display technology relies on integrating light-emitting diodes with display panel as a source for backlighting. In this study, we undertook the challenge of integrating light emitters onto amorphous quartz by demonstrating the direct growth and fabrication of a III-nitride nanowire-based light-emitting diode. The proof-of-concept device exhibits a low turn-on voltage of 2.6 V, on an amorphous quartz substrate. We achieved ~ 40% transparency across the visible wavelength while maintaining electrical conductivity by employing a TiN/Ti interlayer on quartz as a translucent conducting layer. The nanowire-on-quartz LED emits a broad linewidth spectrum of light centered at true yellow color (~ 590 nm), an important wavelength bridging the green-gap in solid-state lighting technology, with significantly less strain and dislocations compared to conventional planar quantum well nitride structures. Our endeavor highlighted the feasibility of fabricating III-nitride optoelectronic device on a scalable amorphous substrate through facile growth and fabrication steps. For practical demonstration, we demonstrated tunable correlated color temperature white light, leveraging on the broadly tunable nanowire spectral characteristics across red-amber-yellow color regime.

Magnetic softening and nanocrystallization in amorphous Co-rich alloys

NASA Astrophysics Data System (ADS)

Buttino, G.; Cecchetti, A.; Poppi, M.

1997-02-01

In this work we have analyzed the changes of the magnetic properties in the Co-based Metglas 2714A (made by Allied Chem. Corp., USA) caused by isothermal heat treatments in the range of temperature from room temperature to conventional crystallization temperature Tcr = 550°C. The nominal composition of the amorphous alloy is Co 66Fe 4Ni 1B 14Si 15. The analysis is made on toroidal samples prepared by winding lengths of amorphous ribbon of about 20 cm. The magnetic properties undergo variations depending on the treatment temperature, except for the saturation magnetization which remains unchanged. For heat treatments of about half an hour around 500°C, superior soft magnetic properties are obtained. Particularly, the initial permeability reaches values up to ten times the value of permeability in the as-received sample. Analysis by the transmission electron microscopy of the sample annealed around 500°C reveals the formation of a nanocrystalline phase, with average grain size of 2 nm, embedded in a residual amorphous matrix. The occurrence of permeability increases in concomitance with the formation of the nanocrystalline phase is ascribed to a drastic reduction in the local magnetocrystalline anisotropy randomly averaged out by the exchange interactions, similar to the case of the annealed Fe-based alloys containing Cu.

An amorphous silicon photodiode with 2 THz gain-bandwidth product based on cycling excitation process

NASA Astrophysics Data System (ADS)

Yan, Lujiang; Yu, Yugang; Zhang, Alex Ce; Hall, David; Niaz, Iftikhar Ahmad; Raihan Miah, Mohammad Abu; Liu, Yu-Hsin; Lo, Yu-Hwa

2017-09-01

Since impact ionization was observed in semiconductors over half a century ago, avalanche photodiodes (APDs) using impact ionization in a fashion of chain reaction have been the most sensitive semiconductor photodetectors. However, APDs have relatively high excess noise, a limited gain-bandwidth product, and high operation voltage, presenting a need for alternative signal amplification mechanisms of superior properties. As an amplification mechanism, the cycling excitation process (CEP) was recently reported in a silicon p-n junction with subtle control and balance of the impurity levels and profiles. Realizing that CEP effect depends on Auger excitation involving localized states, we made the counter intuitive hypothesis that disordered materials, such as amorphous silicon, with their abundant localized states, can produce strong CEP effects with high gain and speed at low noise, despite their extremely low mobility and large number of defects. Here, we demonstrate an amorphous silicon low noise photodiode with gain-bandwidth product of over 2 THz, based on a very simple structure. This work will impact a wide range of applications involving optical detection because amorphous silicon, as the primary gain medium, is a low-cost, easy-to-process material that can be formed on many kinds of rigid or flexible substrates.

Crystallization of amorphous solid dispersions of resveratrol during preparation and storage-Impact of different polymers.

PubMed

Wegiel, Lindsay A; Mauer, Lisa J; Edgar, Kevin J; Taylor, Lynne S

2013-01-01

The objective of this study was to investigate intermolecular interactions between resveratrol and polymers in amorphous blends and to study the potential correlations between compound-polymer interactions, manufacturability, and stability of the amorphous system to crystallization during storage. Polymers included two grades of poly (vinylpyrrolidone) (PVP), Eudragit E100 (E100), hydroxypropyl methylcellulose (HPMC), hydroxypropyl methylcellulose acetate succinate (HPMCAS), carboxymethyl cellulose acetate butyrate, and poly (acrylic acid) (PAA). Amorphous blends ("solid dispersions") were prepared by dissolving both resveratrol and polymer in a solvent followed by rotary evaporation. Crystallinity was evaluated using X-ray powder diffraction and was studied as a function of time. Mid-infrared (IR) spectroscopy was used to investigate resveratrol-polymer interactions. Polymer influence on the crystallization behavior of resveratrol varied and could be correlated to the polymer structure, whereby polymers with good hydrogen bond acceptor groups performed better as crystallization inhibitors. Resveratrol-polymer hydrogen bonding interactions could be inferred from the IR spectra. Somewhat surprisingly, E100 and resveratrol showed evidence of an acid-base reaction, in addition to intermolecular hydrogen bonding interactions. PVP K29/32 appeared to form stronger hydrogen bond interactions with resveratrol relative to HPMC, HPMCAS, and PAA, consistent with acceptor group chemistry. Long-term stability of the systems against crystallization suggested that stability is linked to the type and strength of intermolecular interactions present. whereby resveratrol blended with E100 and PVP K29/32 showed the greatest stability to crystallization. In conclusion, amorphous resveratrol is unstable and difficult to form, requiring the assistance of a polymeric crystallization inhibitor to facilitate the formation of an amorphous solid dispersion. Polymers effective at inhibiting crystallization were identified, and it is rationalized that their effectiveness is based on the type and strength of their intermolecular interactions with resveratrol. Copyright © 2012 Wiley Periodicals, Inc.

The role of stoichiometric vacancy periodicity in pressure-induced amorphization of the Ga{sub 2}SeTe{sub 2} semiconductor alloy

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

Abdul-Jabbar, N. M.; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720; Kalkan, B.

2014-08-04

We observe that pressure-induced amorphization of Ga{sub 2}SeTe{sub 2} (a III-VI semiconductor) is directly influenced by the periodicity of its intrinsic defect structures. Specimens with periodic and semi-periodic two-dimensional vacancy structures become amorphous around 10–11 GPa in contrast to those with aperiodic structures, which amorphize around 7–8 GPa. The result is an instance of altering material phase-change properties via rearrangement of stoichiometric vacancies as opposed to adjusting their concentrations. Based on our experimental findings, we posit that periodic two-dimensional vacancy structures in Ga{sub 2}SeTe{sub 2} provide an energetically preferred crystal lattice that is less prone to collapse under applied pressure. This ismore » corroborated through first-principles electronic structure calculations, which demonstrate that the energy stability of III-VI structures under hydrostatic pressure is highly dependent on the configuration of intrinsic vacancies.« 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.

Modeling of grain-oriented Si-steel and amorphous alloy iron core under ferroresonance using Jiles-Atherton hysteresis method

NASA Astrophysics Data System (ADS)

Sima, Wenxia; Zou, Mi; Yang, Ming; Yang, Qing; Peng, Daixiao

2018-05-01

Amorphous alloy is increasingly widely used in the iron core of power transformer due to its excellent low loss performance. However, its potential harm to the power system is not fully studied during the electromagnetic transients of the transformer. This study develops a simulation model to analyze the effect of transformer iron core materials on ferroresonance. The model is based on the transformer π equivalent circuit. The flux linkage-current (ψ-i) Jiles-Atherton reactor is developed in an Electromagnetic Transients Program-Alternative Transients Program and is used to represent the magnetizing branches of the transformer model. Two ferroresonance cases are studied to compare the performance of grain-oriented Si-steel and amorphous alloy cores. The ferroresonance overvoltage and overcurrent are discussed under different system parameters. Results show that amorphous alloy transformer generates higher voltage and current than those of grain-oriented Si-steel transformer and significantly harms the power system safety.

Model for determination of mid-gap states in amorphous metal oxides from thin film transistors

NASA Astrophysics Data System (ADS)

Bubel, S.; Chabinyc, M. L.

2013-06-01

The electronic density of states in metal oxide semiconductors like amorphous zinc oxide (a-ZnO) and its ternary and quaternary oxide alloys with indium, gallium, tin, or aluminum are different from amorphous silicon, or disordered materials such as pentacene, or P3HT. Many ZnO based semiconductors exhibit a steep decaying density of acceptor tail states (trap DOS) and a Fermi level (EF) close to the conduction band energy (EC). Considering thin film transistor (TFT) operation in accumulation mode, the quasi Fermi level for electrons (Eq) moves even closer to EC. Classic analytic TFT simulations use the simplification EC-EF> `several'kT and cannot reproduce exponential tail states with a characteristic energy smaller than 1/2 kT. We demonstrate an analytic model for tail and deep acceptor states, valid for all amorphous metal oxides and include the effect of trap assisted hopping instead of simpler percolation or mobility edge models, to account for the observed field dependent mobility.

Preservation of amorphous ultrafine material: A proposed proxy for slip during recent earthquakes on active faults

PubMed Central

Hirono, Tetsuro; Asayama, Satoru; Kaneki, Shunya; Ito, Akihiro

2016-01-01

The criteria for designating an “Active Fault” not only are important for understanding regional tectonics, but also are a paramount issue for assessing the earthquake risk of faults that are near important structures such as nuclear power plants. Here we propose a proxy, based on the preservation of amorphous ultrafine particles, to assess fault activity within the last millennium. X-ray diffraction data and electron microscope observations of samples from an active fault demonstrated the preservation of large amounts of amorphous ultrafine particles in two slip zones that last ruptured in 1596 and 1999, respectively. A chemical kinetic evaluation of the dissolution process indicated that such particles could survive for centuries, which is consistent with the observations. Thus, preservation of amorphous ultrafine particles in a fault may be valuable for assessing the fault’s latest activity, aiding efforts to evaluate faults that may damage critical facilities in tectonically active zones. PMID:27827413

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.

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.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Amorphous TiO2 Shells: A Vital Elastic Buffering Layer on Silicon Nanoparticles for High-Performance and Safe Lithium Storage.

PubMed

Yang, Jianping; Wang, Yunxiao; Li, Wei; Wang, Lianjun; Fan, Yuchi; Jiang, Wan; Luo, Wei; Wang, Yang; Kong, Biao; Selomulya, Cordelia; Liu, Hua Kun; Dou, Shi Xue; Zhao, Dongyuan

2017-12-01

Smart surface coatings of silicon (Si) nanoparticles are shown to be good examples for dramatically improving the cyclability of lithium-ion batteries. Most coating materials, however, face significant challenges, including a low initial Coulombic efficiency, tedious processing, and safety assessment. In this study, a facile sol-gel strategy is demonstrated to synthesize commercial Si nanoparticles encapsulated by amorphous titanium oxide (TiO 2 ), with core-shell structures, which show greatly superior electrochemical performance and high-safety lithium storage. The amorphous TiO 2 shell (≈3 nm) shows elastic behavior during lithium discharging and charging processes, maintaining high structural integrity. Interestingly, it is found that the amorphous TiO 2 shells offer superior buffering properties compared to crystalline TiO 2 layers for unprecedented cycling stability. Moreover, accelerating rate calorimetry testing reveals that the TiO 2 -encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Controlling the crystallization and magnetic properties of melt-spun Pr2Fe14B/α-Fe nanocomposites by Joule heating

NASA Astrophysics Data System (ADS)

Jin, Z. Q.; Cui, B. Z.; Liu, J. P.; Ding, Y.; Wang, Z. L.; Thadhani, N. N.

2004-05-01

Pr2Fe14B/α-Fe based nanocomposites have been prepared through crystallization of melt-spun amorphous Pr7Tb1Fe85Nb0.5Zr0.5B6 ribbons by means of ac Joule heating while simultaneously monitoring room-temperature electrical resistance R. The R value shows a strong variation with respect to applied current I, and is closely related to the amorphous-to-nanocrystalline phase transformation. The curve of R versus I allows one to control the crystallization behavior during Joule heating and to identify the heat-treatment conditions for optimum magnetic properties. A coercivity of 550 kA/m and a maximum energy product of 128 kJ/m3 have been obtained upon heating the amorphous ribbons at a current of 2.0 A. These properties are around 30% higher than the values of samples prepared by conventionally (furnace) annealed amorphous ribbons.

Mechanism for amorphization of boron carbide under complex stress conditions

NASA Astrophysics Data System (ADS)

Li, Jun; Xu, Shuang; Liu, Lisheng; Wang, Zhen; Zhang, Jinyong; Liu, Qiwen

2018-05-01

As an excellent material, the application of boron carbide (B4C) is limited by pressure-induced amorphization. To understand the mechanism for amorphization in B4C, first-principles methods based on density functional theory were employed to investigate the mechanical behaviors and the deformation process in B4C under complex stress conditions with six different biaxial perpendicular compression directions. The angle (θ) between one of the loading directions and the [0 0 0 1] c-axis ranged from 0° to 75° with every 15° interval. We found that the maximum stress at θ = 30° is 124.5 GPa, which is the lowest among six biaxial compressions. Simulation results show that the mechanism for amorphization in B4C under complex stress conditions is complicated. We take the θ = 30° biaxial compression as an example to explain the complicated deformation process. In the elastic deformation region, sudden bending of three-atom chains occurs and results in a stress fluctuation. Then the formation of new B–B bonds between the three-atom chains and the icosahedra leads to the first stress drop. After that, the B–C bonds in the chains are broken, resulting in the second stress drop. In this process, the icosahedra are partially destroyed. The stress increases continuously and then drops at the critical failure strain. Finally, the fully destruction of icosahedra leads to amorphization in B4C. However, under other five biaxial compressions, the B–C bonds in three-atom chains are not fractured before structural failure. Understanding the deformation mechanism for amorphization of B4C in real applications is prime important for proposing how to resist amorphization and enhance the toughness of B4C.

A Step toward High-Energy Silicon-Based Thin Film Lithium Ion Batteries.

PubMed

Reyes Jiménez, Antonia; Klöpsch, Richard; Wagner, Ralf; Rodehorst, Uta C; Kolek, Martin; Nölle, Roman; Winter, Martin; Placke, Tobias

2017-05-23

The next generation of lithium ion batteries (LIBs) with increased energy density for large-scale applications, such as electric mobility, and also for small electronic devices, such as microbatteries and on-chip batteries, requires advanced electrode active materials with enhanced specific and volumetric capacities. In this regard, silicon as anode material has attracted much attention due to its high specific capacity. However, the enormous volume changes during lithiation/delithiation are still a main obstacle avoiding the broad commercial use of Si-based electrodes. In this work, Si-based thin film electrodes, prepared by magnetron sputtering, are studied. Herein, we present a sophisticated surface design and electrode structure modification by amorphous carbon layers to increase the mechanical integrity and, thus, the electrochemical performance. Therefore, the influence of amorphous C thin film layers, either deposited on top (C/Si) or incorporated between the amorphous Si thin film layers (Si/C/Si), was characterized according to their physical and electrochemical properties. The thin film electrodes were thoroughly studied by means of electrochemical impedance spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. We can show that the silicon thin film electrodes with an amorphous C layer showed a remarkably improved electrochemical performance in terms of capacity retention and Coulombic efficiency. The C layer is able to mitigate the mechanical stress during lithiation of the Si thin film by buffering the volume changes and to reduce the loss of active lithium during solid electrolyte interphase formation and cycling.

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

USGS Publications Warehouse

Hein, J.R.; Schulz, M.S.; Dunham, R.E.; Stern, R.J.; Bloomer, S.H.

2008-01-01

Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 ?? and 7 ?? manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean-8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along, the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms. Copyright 2008 by the American Geophysical Union.

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

NASA Astrophysics Data System (ADS)

Hein, James R.; Schulz, Marjorie S.; Dunham, Rachel E.; Stern, Robert J.; Bloomer, Sherman H.

2008-08-01

Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 Å and 7 Å manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean 8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms.

Physical stability of drugs after storage above and below the glass transition temperature: Relationship to glass-forming ability.

PubMed

Alhalaweh, Amjad; Alzghoul, Ahmad; Mahlin, Denny; Bergström, Christel A S

2015-11-10

Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

Examination of the temperature dependent electronic behavior of GeTe for switching applications

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

Champlain, James G.; Ruppalt, Laura B.; Guyette, Andrew C.

2016-06-28

The DC and RF electronic behaviors of GeTe-based phase change material switches as a function of temperature, from 25 K to 375 K, have been examined. In its polycrystalline (ON) state, GeTe behaved as a degenerate p-type semiconductor, exhibiting metal-like temperature dependence in the DC regime. This was consistent with the polycrystalline (ON) state RF performance of the switch, which exhibited low resistance S-parameter characteristics. In its amorphous (OFF) state, the GeTe presented significantly greater DC resistance that varied considerably with bias and temperature. At low biases (<1 V) and temperatures (<200 K), the amorphous GeTe low-field resistance dramatically increased, resulting in exceptionally highmore » amorphous-polycrystalline (OFF-ON) resistance ratios, exceeding 10{sup 9} at cryogenic temperatures. At higher biases and temperatures, the amorphous GeTe exhibited nonlinear current-voltage characteristics that were best fit by a space-charge limited conduction model that incorporates the effect of a defect band. The observed conduction behavior suggests the presence of two regions of localized traps within the bandgap of the amorphous GeTe, located at approximately 0.26–0.27 eV and 0.56–0.57 eV from the valence band. Unlike the polycrystalline state, the high resistance DC behavior of amorphous GeTe does not translate to the RF switch performance; instead, a parasitic capacitance associated with the RF switch geometry dominates OFF state RF transmission.« less

Applying state diagrams to food processing and development

NASA Technical Reports Server (NTRS)

Roos, Y.; Karel, M.

1991-01-01

The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.

Mixed-Mode Operation of Hybrid Phase-Change Nanophotonic Circuits.

PubMed

Lu, Yegang; Stegmaier, Matthias; Nukala, Pavan; Giambra, Marco A; Ferrari, Simone; Busacca, Alessandro; Pernice, Wolfram H P; Agarwal, Ritesh

2017-01-11

Phase change materials (PCMs) are highly attractive for nonvolatile electrical and all-optical memory applications because of unique features such as ultrafast and reversible phase transitions, long-term endurance, and high scalability to nanoscale dimensions. Understanding their transient characteristics upon phase transition in both the electrical and the optical domains is essential for using PCMs in future multifunctional optoelectronic circuits. Here, we use a PCM nanowire embedded into a nanophotonic circuit to study switching dynamics in mixed-mode operation. Evanescent coupling between light traveling along waveguides and a phase-change nanowire enables reversible phase transition between amorphous and crystalline states. We perform time-resolved measurements of the transient change in both the optical transmission and resistance of the nanowire and show reversible switching operations in both the optical and the electrical domains. Our results pave the way toward on-chip multifunctional optoelectronic integrated devices, waveguide integrated memories, and hybrid processing applications.

Developing a High Fidelity Martian Soil Simulant Based on MSL Measurements: Applications for Habitability, Exploration, and In-Situ Resource Utilization

NASA Astrophysics Data System (ADS)

Cannon, K.; Britt, D. T.; Smith, T. M.; Fritsche, R. F.; Covey, S. D.; Batcheldor, D.; Watson, B.

2017-12-01

Powerful instruments, that include CheMin and SAM on the MSL Curiosity rover, have provided an unprecedented look into the mineral, chemical, and volatile composition of Martian soils. Interestingly, the bulk chemistry of the Rocknest windblown soil is a close match to similar measurements from the Spirit and Opportunity rovers, suggesting the presence of a global basaltic soil component. The Martian regolith is likely composed of this global soil mixed with locally to regionally derived components that include alteration products and evolved volcanic compositions. Without returned soil samples, researchers have relied on terrestrial simulants to address fundamental Mars science, habitability, in-situ resource utilization, and hardware for future exploration. However, these past simulants have low fidelity compared to actual Martian soils: JSC Mars-1a is an amorphous palagonitic material with spectral similarities to Martian dust, not soil, and Mojave Mars is simply a ground up terrestrial basalt chosen for its convenient location. Based on our experience creating asteroid regolith simulants, we are developing a high fidelity Martian soil simulant (Mars Global) designed ab initio to match the mineralogy, chemistry, and volatile contents of the global basaltic soil on Mars. The crystalline portion of the simulant is based on CheMin measurements of Rocknest and includes plagioclase, two pyroxenes, olivine, hematite, magnetite, anhydrite, and quartz. The amorphous portion is less well constrained, but we are re-creating it with basaltic glass, synthetic ferrihydrite, ferric sulfate, and carbonates. We also include perchlorate and nitrate salts based on evolved gas analyses from the SAM instrument. Analysis and testing of Mars Global will include physical properties (shear strength, density, internal friction angle), spectral properties, magnetic properties, and volatile release patterns. The simulant is initially being designed for NASA agricultural studies, but applications include studies of habitability, toxicity, and in-situ resource utilization, among others. Through a partnership with Deep Space Industries we intend to produce industrial quantities of Mars Global from consistently maintained feedstocks, making it available to researchers, engineers, and educators.

Conceptual design of a lunar base solar power plant lunar base systems study task 3.3

NASA Technical Reports Server (NTRS)

1988-01-01

The best available concepts for a 100 kW Solar Lunar Power Plant based on static and dynamic conversion concepts have been examined. The two concepts which emerged for direct comparison yielded a difference in delivered mass of 35 MT, the mass equivalent of 1.4 lander payloads, in favor of the static concept. The technologies considered for the various elements are either state-of-the-art or near-term. Two photovoltaic cell concepts should receive high priority for development: i.e., amorphous silicon and indium phosphide cells. The amorphous silicon, because it can be made so light weight and rugged; and the indium phosphide, because it shows very high efficiency potential and is reportedly not degraded by radiation. Also the amorphous silicon cells may be mounted on flexible backing that may roll up much like a carpet for compact storage, delivery, and ease of deployment at the base. The fuel cell and electrolysis cell technology is quite well along for lunar base applications, and because both the Shuttle and the forthcoming Space Station incorporate these devices, the status quo will be maintained. Early development of emerging improvements should be implemented so that essential life verification test programs may commence.

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.

Optoelectronic properties of novel amorphous CuAlO2/ZnO NWs based heterojunction

NASA Astrophysics Data System (ADS)

Bu, Ian Y. Y.

2013-08-01

Amorphous p-type CuAlO2 thin films were grown onto n-type crystalline ZnO NWs forming a heterojunction through the combination of sol-gel process and hydrothermal growth method. The effects of temperature on structure and optoelectronic properties of CuAlO2 thin films were investigated through various measurement techniques. It was found that the derived CuAlO2 is Al-rich with thin film. UV-Vis measurements showed that the deposited CuAlO2 films are semi-transparent with maximum transmittance ∼82% at 500 nm. Electrical characterization and integration into pn junction confirms that the amorphous CuAlO2 is p-type and exhibited photovoltaic behavior.

Amorphous In-Ga-Zn-O Thin Film Transistor Current-Scaling Pixel Electrode Circuit for Active-Matrix Organic Light-Emitting Displays

NASA Astrophysics Data System (ADS)

Chen, Charlene; Abe, Katsumi; Fung, Tze-Ching; Kumomi, Hideya; Kanicki, Jerzy

2009-03-01

In this paper, we analyze application of amorphous In-Ga-Zn-O thin film transistors (a-InGaZnO TFTs) to current-scaling pixel electrode circuit that could be used for 3-in. quarter video graphics array (QVGA) full color active-matrix organic light-emitting displays (AM-OLEDs). Simulation results, based on a-InGaZnO TFT and OLED experimental data, show that both device sizes and operational voltages can be reduced when compare to the same circuit using hydrogenated amorphous silicon (a-Si:H) TFTs. Moreover, the a-InGaZnO TFT pixel circuit can compensate for the drive TFT threshold voltage variation (ΔVT) within acceptable operating error range.

Magnetic and electrical properties of several Mn-based amorphous alloys

NASA Astrophysics Data System (ADS)

Obi, Y.; Morita, H.; Fujimori, H.

1987-03-01

Magnetic and electrical properties of amorphous Mn-Y, Mn-Zr, and Mn-Nb alloys have been investigated. All these alloys have a temperature-dependent susceptibility which is well fitted by a Curie-Weiss law. This implies the existence of localized magnetic moments associated with the Mn atoms. In addition, amorphous Mn-Y alloys exhibit spin-glass characteristics at low temperature. The experimental results of the electrical resistivity show that the temperature coefficient of resistivity (TCR) of both Mn-Y and Mn-Zr are negative, while Mn-Nb has a positive TCR. On the other hand, the resistivity-temperature curves of Mn-Zr and Mn-Nb have nearly the same tendency but are different from that of Mn-Y.

Controllable film densification and interface flatness for high-performance amorphous indium oxide based thin film transistors

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

Ou-Yang, Wei, E-mail: OUYANG.Wei@nims.go.jp, E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Mitoma, Nobuhiko; Kizu, Takio

2014-10-20

To avoid the problem of air sensitive and wet-etched Zn and/or Ga contained amorphous oxide transistors, we propose an alternative amorphous semiconductor of indium silicon tungsten oxide as the channel material for thin film transistors. In this study, we employ the material to reveal the relation between the active thin film and the transistor performance with aid of x-ray reflectivity study. By adjusting the pre-annealing temperature, we find that the film densification and interface flatness between the film and gate insulator are crucial for achieving controllable high-performance transistors. The material and findings in the study are believed helpful for realizingmore » controllable high-performance stable transistors.« less

High resistivity iron-based, thermally stable magnetic material for on-chip integrated inductors

DOEpatents

Deligianni, Hariklia; Gallagher, William J.; Mason, Maurice; O'Sullivan, Eugene J.; Romankiw, Lubomyr T.; Wang, Naigang

2017-03-07

An on-chip magnetic structure includes a palladium activated seed layer and a substantially amorphous magnetic material disposed onto the palladium activated seed layer. The substantially amorphous magnetic material includes nickel in a range from about 50 to about 80 atomic % (at. %) based on the total number of atoms of the magnetic material, iron in a range from about 10 to about 50 at. % based on the total number of atoms of the magnetic material, and phosphorous in a range from about 0.1 to about 30 at. % based on the total number of atoms of the magnetic material. The magnetic material can include boron in a range from about 0.1 to about 5 at. % based on the total number of atoms of the magnetic material.

Curcumin-Eudragit® E PO solid dispersion: A simple and potent method to solve the problems of curcumin.

PubMed

Li, Jinglei; Lee, Il Woo; Shin, Gye Hwa; Chen, Xiguang; Park, Hyun Jin

2015-08-01

Using a simple solution mixing method, curcumin was dispersed in the matrix of Eudragit® E PO polymer. Water solubility of curcumin in curcumin-Eudragit® E PO solid dispersion (Cur@EPO) was greatly increased. Based on the results of several tests, curcumin was demonstrated to exist in the polymer matrix in amorphous state. The interaction between curcumin and the polymer was investigated through Fourier transform infrared spectroscopy and (1)H NMR which implied that OH group of curcumin and carbonyl group of the polymer involved in the H bonding formation. Cur@EPO also provided protection function for curcumin as verified by the pH challenge and UV irradiation test. The pH value influenced curcumin release profile in which sustained release pattern was revealed. Additionally, in vitro transdermal test was conducted to assess the potential of Cur@EPO as a vehicle to deliver curcumin through this alternative administration route. Copyright © 2015 Elsevier B.V. All rights reserved.

Comprehensive insights into the structural and chemical changes in mixed-anion FeOF electrodes by using operando PDF and NMR spectroscopy.

PubMed

Wiaderek, Kamila M; Borkiewicz, Olaf J; Castillo-Martínez, Elizabeth; Robert, Rosa; Pereira, Nathalie; Amatucci, Glenn G; Grey, Clare P; Chupas, Peter J; Chapman, Karena W

2013-03-13

In-depth analysis of operando X-ray pair distribution function (PDF) data is combined with Li NMR spectroscopy to gain comprehensive insights into the electrochemical reaction mechanism of high-performance iron oxyfluoride electrodes. While the full discharge capacity could be recovered upon charge, implying reversibility of the electrochemical reaction, the atomic structure of the electrode formed after cycling (discharge-charge) differs from the pristine uncycled electrode material. Instead, the "active" electrode that forms upon cycling is a nanocomposite of an amorphous rutile phase and a nanoscale rock salt phase. Bond valence sum analysis, based on the precise structural parameters (bond lengths and coordination number) extracted from the in situ PDF data, suggests that anion partitioning occurs during the electrochemical reaction, with the rutile phase being F-rich and the rock salt phase being O-rich. The F- and O-rich phases react sequentially; Fe in a F-rich environment reacts preferentially during both discharge and charge.

Silicon Nanosheets: Crossover between Multilayer Silicene and Diamond-like Growth Regime.

PubMed

Grazianetti, Carlo; Cinquanta, Eugenio; Tao, Li; De Padova, Paola; Quaresima, Claudio; Ottaviani, Carlo; Akinwande, Deji; Molle, Alessandro

2017-03-28

The structural and electronic properties of nanoscale Si epitaxially grown on Ag(111) can be tuned from a multilayer silicene phase, where the constitutive layers incorporate a mixed sp 2 /sp 3 bonding, to other ordinary Si phases, such as amorphous and diamond-like Si. Based on comparative scanning tunneling microscopy and Raman spectroscopy investigations, a key role in determining the nanoscale Si phase is played by the growth temperature of the epitaxial deposition on Ag(111) substrate and the presence or absence of a single-layer silicene as a seed for the successive growth. Furthermore, when integrated into a field-effect transistor device, multilayer silicene exhibits a characteristic ambipolar charge carrier transport behavior that makes it strikingly different from other conventional Si channels and suggestive of a Dirac-like character of the electronic bands of the crystal. These findings spotlight the interest in multilayer silicene as a different nanoscale Si phase for advanced nanotechnology applications such as ultrascaled nanoelectronics and nanomembranes, as well as for fundamental exploration of quantum properties.

Study of interaction in silica glass via model potential approach

NASA Astrophysics Data System (ADS)

Mann, Sarita; Rani, Pooja

2016-05-01

Silica is one of the most commonly encountered substances in daily life and in electronics industry. Crystalline SiO2 (in several forms: quartz, cristobalite, tridymite) is an important constituent of many minerals and gemstones, both in pure form and mixed with related oxides. Cohesive energy of amorphous SiO2 has been investigated via intermolecular potentials i.e weak Van der Waals interaction and Morse type short-range interaction. We suggest a simple atom-atom based Van der Waals as well as Morse potential to find cohesive energy of glass. It has been found that the study of silica structure using two different model potentials is significantly different. Van der Waals potential is too weak (P.E =0.142eV/molecule) to describe the interaction between silica molecules. Morse potential is a strong potential, earlier given for intramolecular bonding, but if applied for intermolecular bonding, it gives a value of P.E (=-21.92eV/molecule) to appropriately describe the structure of silica.

Origin of the Mariano Lake uranium deposit, McKinley County, New Mexico

USGS Publications Warehouse

Fishman, Neil S.; Reynolds, Richard L.

1982-01-01

The Mariano Lake uranium deposit, hosted by the Brushy Basin Member of the Jurassic Morrison Formation, occurs in the trough of an east-west trending syncline at the western end of the Smith Lake-Mariano Lake group of uranium deposits near Crownpoint, New Mexico. The orebody, which contains abundant amorphous organic material, is situated on the reduced side of a regional reduction-oxidation (redox) interface. The presence of amorphous organic material suggests the orebody may represent a tabular (primary) deposit, whereas the close proximity of the orebody to the redox interface is suggestive that uranium was secondarily redistributed by oxidative processes from pre-existing tabular orebodies. Uranium contents correlate positively with both organic carbon and vanadium contents. Petrographic evidence and scanning electron microscope-energy dispersive analyses point to uranium residence in the epigentically introduced amorphous organic material, which coats detrital grains and fills voids. Uranium mineralization was preceded by the following diagenetic alterations: precipitation of pyrite (d34S values ranging from-11.0 to-38.2 per mil); precipitation of mixed-layer smectite-illite clays; partial dissolution of some of the detrital feldspar population; and precipitation of quartz and adularia overgrowths. Alterations associated with uranium mineralization include emplacement of amorphous organic material (possibly uranium bearing); destruction of detrital iron-titanium oxide grains; coprecipitation of chlorite and microcrystalline quartz, and precipitation of pyrite and marcasite (d34S values for these sulfides ranging from -29.4 to -41.6 per mil). After mineralization, calcite, dolomite, barite, and kaolinite precipitated, and authigenic iron disulfides were replaced by ferric oxides and hydroxides. Geochemical data (primarily the positive correlation of uranium content to both organic carbon and vanadium contents) and petrographic observations (epigentically introduced amorphous organic matter and uranium residence in this organic matter) indicate that the Mariano Lake orebody is a tabular-type uranium deposit. Oxidative processes have not noticeably redistributed and reconcentrated primary uranium in the immediate vicinity of the deposit nor have they greatly modified geochemical characteristics in the ore. Preservation of the Mariano Lake deposit may not only be related to its position along the synclinal trough, where oxidative destruction of the orebody has been inhibited by stagnation of oxidizing ground waters by the structure, but also due to the deflection of ground waters (resulting from low orebody porosity) around the orebody.

The influence of Sc addition on the welding microstructure of Zr-based bulk metallic glass: The stability of the amorphous phase

NASA Astrophysics Data System (ADS)

Wang, Shing Hoa; Kuo, Pei Hung; Tsang, Hsiao Tsung; Jeng, Rong Ruey; Lin, Yu Lon

2007-10-01

Pulsed direct current autogeneous tungsten inert gas arc welding was conducted on rods of bulk metallic glasses (BMGs) Zr55Cu30Ni5Al10 and (Zr55Cu30Ni5Al10)99.98Sc0.02 under two different cooling conditions. The crystalline precipitates in the fusion zone of BMG Zr55Cu30Ni5Al10 were confirmed by microfocused x-ray diffraction pattern analysis as Zr2Ni and Zr2(Cu,Al) intermetallic compounds. In contrast, BMG with Sc addition (Zr55Cu30Ni5Al10)99.98Sc0.02 shows an excellent stable glass forming ability. The fusion zone of BMG (Zr55Cu30Ni5Al10)99.98Sc0.02 remains in the same amorphous state as that of the amorphous base metal when the weld is cooled with accelerated cooling.

Decoupling the Effects of Mass Density and Hydrogen-, Oxygen-, and Aluminum-Based Defects on Optoelectronic Properties of Realistic Amorphous Alumina.

PubMed

Riffet, Vanessa; Vidal, Julien

2017-06-01

The search for functional materials is currently hindered by the difficulty to find significant correlation between constitutive properties of a material and its functional properties. In the case of amorphous materials, the diversity of local structures, chemical composition, impurities and mass densities makes such a connection difficult to be addressed. In this Letter, the relation between refractive index and composition has been investigated for amorphous AlO x materials, including nonstoichiometric AlO x , emphasizing the role of structural defects and the absence of effect of the band gap variation. It is found that the Newton-Drude (ND) relation predicts the refractive index from mass density with a rather high level of precision apart from some structures displaying structural defects. Our results show especially that O- and Al-based defects act as additive local disturbance in the vicinity of band gap, allowing us to decouple the mass density effects from defect effects (n = n[ND] + Δn defect ).

Wide Temperature Core Loss Characteristics of Transverse Magnetically Annealed Amorphous Tapes for High Frequency Aerospace Magnetics

NASA Technical Reports Server (NTRS)

Niedra, Janis M.; Schwarze, Gene E.

1999-01-01

100 kHz core loss properties of sample transverse magnetically annealed, cobalt-based amorphous and iron-based nanocrystalline tape wound magnetic cores are presented over the temperature range of -150 C to 150 C, at selected values of B(sub peak). For B-fields not close to saturation, the core loss is not sensitive to temperature in this range and is as low as seen in the best MnZn power ferrites at their optimum temperatures. Frequency resolved characteristics are given over the range of 50 kHz to 1 MHz, but at B(sub peak) = 0.1 T and 50 C only. For example, the 100 kHz specific core loss ranged from 50 - 70 mW/cubic cm for the 3 materials, when measured at 0.1 T and 50 C. This very low high frequency core loss, together with near zero saturation magnetostriction and insensitivity to rough handling, makes these amorphous ribbons strong candidates for power magnetics applications in wide temperature aerospace environments.

R&D issues in scale-up and manufacturing of amorphous silicon tandem modules

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

Arya, R.R.; Carlson, D.E.; Chen, L.F.

1999-03-01

R & D on amorphous silicon based tandem junction devices has improved the throughtput, the material utilization, and the performance of devices on commercial tin oxide coated glass. The tandem junction technology has been scaled-up to produce 8.6&hthinsp;Ft{sup 2} monolithically integrated modules in manufacturing at the TF1 plant. Optimization of performance and stability of these modules is ongoing. {copyright} {ital 1999 American Institute of Physics.}

Semitransparent conductive carbon films synthesized by sintering spin-coated sp3-based network polymer

NASA Astrophysics Data System (ADS)

Yanase, Takashi; Uwabe, Hiroaki; Hasegawa, Koki; Nagahama, Taro; Yamaguchi, Makoto; Shimada, Toshihiro

2018-03-01

We synthesized semitransparent conducting thin films of amorphous carbon from sp3-rich network polymer. The films showed a reasonable optical transparency (58-73% transmission in the wavelength range of 380-2200 nm), a low electric resistivity (6.7 × 10-3 Ω cm), and durability against corrosive chemical reagents. The sintering of the amorphous films results in the formation of a carbon honeycomb lattice in the films.

Nucleation in Sheared Granular Matter

NASA Astrophysics Data System (ADS)

Rietz, Frank; Radin, Charles; Swinney, Harry L.; Schröter, Matthias

2018-02-01

We present an experiment on crystallization of packings of macroscopic granular spheres. This system is often considered to be a model for thermally driven atomic or colloidal systems. Cyclically shearing a packing of frictional spheres, we observe a first order phase transition from a disordered to an ordered state. The ordered state consists of crystallites of mixed fcc and hcp symmetry that coexist with the amorphous bulk. The transition, initiated by homogeneous nucleation, overcomes a barrier at 64.5% volume fraction. Nucleation consists predominantly of the dissolving of small nuclei and the growth of nuclei that have reached a critical size of about ten spheres.

Systematic Examination of Stardust Bulbous Track Wall Materials

NASA Technical Reports Server (NTRS)

Nakamura-Messenger, K.; Clemett, S. J.; Nguyen, A. N.; Berger, E. L.; Keller, L. P.; Messenger, S.

2013-01-01

Analyses of Comet Wild-2 samples returned by NASA's Stardust spacecraft have focused primarily on terminal particles (TPs) or well-preserved fine-grained materials along the track walls [1,2]. However much of the collected material was melted and mixed intimately with the aerogel by the hypervelocity impact [3,4]. We are performing systematic examinations of entire Stardust tracks to establish the mineralogy and origins of all comet Wild 2 components [7,8]. This report focuses on coordinated analyses of indigenous crystalline and amorphous/melt cometary materials along the aerogel track walls, their interaction with aerogel during collection and comparisons with their TPs.

Deuteron NMR (Nuclear Magnetic Resonance) in relation to the glass transition in polymers

NASA Technical Reports Server (NTRS)

Roessler, E.; Sillescu, H.; Spiess, H. W.; Wallwitz, R.

1983-01-01

H-2NMR is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare H-2 spin alignment echo spectra of chain deuterated polystyrene with model calculations for restricted rotational Brownian motion. Molecular motion in the polyztyrene-toluene system has been investigated by analyzing H-2NMR of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into solid and liquid components where the respective average correlation times differ by more than 5 decades.

Ammonia formation caused by the presence of water in the wet grinding of silicon nitride powder

NASA Technical Reports Server (NTRS)

Kanno, Y.; Suzuki, K.; Kuwahara, Y.

1984-01-01

Si3 N4 powder (amorphous, alpha-, and beta-Si3 N4) was mixed with MeOH containing 8.87 mol. % H2O and ground. The NH3 generation rapidly increased after a grinding time of 100 hours. Silicon nitride sintered material was chosen as one of the high temperature, high strength structural materials and studies of the control of the raw material powder, preparation of the sintered body (finding the right assistant, hot press, high pressure sintering, fracture toughness and oxidation at high temperature were performed.

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.

Water clusters in amorphous pharmaceuticals.

PubMed

Authelin, Jean-Rene; MacKenzie, Alan P; Rasmussen, Don H; Shalaev, Evgenyi Y

2014-09-01

Amorphous materials, although lacking the long-range translational and rotational order of crystalline and liquid crystalline materials, possess certain local (short-range) structure. This paper reviews the distribution of one particular component present in all amorphous pharmaceuticals, that is, water. Based on the current understanding of the structure of water, water molecules can exist in either unclustered form or as aggregates (clusters) of different sizes and geometries. Water clusters are reported in a range of amorphous systems including carbohydrates and their aqueous solutions, synthetic polymers, and proteins. Evidence of water clustering is obtained by various methods that include neutron and X-ray scattering, molecular dynamics simulation, water sorption isotherm, concentration dependence of the calorimetric Tg , dielectric relaxation, and nuclear magnetic resonance. A review of the published data suggests that clustering depends on water concentration, with unclustered water molecules existing at low water contents, whereas clusters form at intermediate water contents. The transition from water clusters to unclustered water molecules can be expected to change water dependence of pharmaceutical properties, such as rates of degradation. We conclude that a mechanistic understanding of the impact of water on the stability of amorphous pharmaceuticals would require systematic studies of water distribution and clustering, while such investigations are lacking. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

Gelatin Nano-coating for Inhibiting Surface Crystallization of Amorphous Drugs.

PubMed

Teerakapibal, Rattavut; Gui, Yue; Yu, Lian

2018-01-05

Inhibit the fast surface crystallization of amorphous drugs with gelatin nano-coatings. The free surface of amorphous films of indomethacin or nifedipine was coated by a gelatin solution (type A or B) and dried. The coating's effect on surface crystallization was evaluated. Coating thickness was estimated from mass change after coating. For indomethacin (weak acid, pK a  = 4.5), a gelatin coating of either type deposited at pH 5 and 10 inhibited its fast surface crystal growth. The coating thickness was 20 ± 10 nm. A gelatin coating deposited at pH 3, however, provided no protective effect. These results suggest that an effective gelatin coating does not require that the drug and the polymer have opposite charges. The ineffective pH 3 coating might reflect the poor wetting of indomethacin's neutral, hydrophobic surface by the coating solution. For nifedipine (weak base, pK a  = 2.6), a gelatin coating of either type deposited at pH 5 inhibited its fast surface crystal growth. Gelatin nano-coatings can be conveniently applied to amorphous drugs from solution to inhibit fast surface crystallization. Unlike strong polyelectrolyte coatings, a protective gelatin coating does not require strict pairing of opposite charges. This could make gelatin coating a versatile, pharmaceutically acceptable coating for stabilizing amorphous drugs.

Impacts of compression on crystallization behavior of freeze-dried amorphous sucrose.

PubMed

Imamura, Koreyoshi; Nomura, Mayo; Tanaka, Kazuhiro; Kataoka, Nobuhide; Oshitani, Jun; Imanaka, Hiroyuki; Nakanishi, Kazuhiro

2010-03-01

An amorphous matrix comprised of sugar molecules is used as excipient and stabilizing agent for labile ingredients in the pharmaceutical industry. The amorphous sugar matrix is often compressed into a tablet form to reduce the volume and improve handling. Herein, the effect of compression on the crystallization behavior of an amorphous sucrose matrix was investigated. Amorphous sucrose samples were prepared by freeze-drying and compressed under different conditions, followed by analyses by differential scanning calorimetry, isothermal crystallization tests, X-ray powder diffractometry, Fourier transform infrared spectroscopy (FTIR), and gas pycnometry. The compressed sample had a lower crystallization temperature and a shorter induction period for isothermal crystallization, indicating that compression facilitates the formation of the critical nucleus of a sucrose crystal. Based on FTIR and molecular dynamics simulation results, the conformational distortion of sucrose molecules due to the compression appears to contribute to the increase in the free energy of the system, which leads to the facilitation of critical nucleus formation. An isothermal crystallization test indicated an increase in the growth rate of sucrose crystals by the compression. This can be attributed to the transformation of the microstructure from porous to nonporous, as the result of compression. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Applications in the Nuclear Industry for Thermal Spray Amorphous Metal and Ceramic Coatings

NASA Astrophysics Data System (ADS)

Blink, J.; Farmer, J.; Choi, J.; Saw, C.

2009-06-01

Amorphous metal and ceramic thermal spray coatings have been developed with excellent corrosion resistance and neutron absorption. These coatings, with further development, could be cost-effective options to enhance the corrosion resistance of drip shields and waste packages, and limit nuclear criticality in canisters for the transportation, aging, and disposal of spent nuclear fuel. Iron-based amorphous metal formulations with chromium, molybdenum, and tungsten have shown the corrosion resistance believed to be necessary for such applications. Rare earth additions enable very low critical cooling rates to be achieved. The boron content of these materials and their stability at high neutron doses enable them to serve as high efficiency neutron absorbers for criticality control. Ceramic coatings may provide even greater corrosion resistance for waste package and drip shield applications, although the boron-containing amorphous metals are still favored for criticality control applications. These amorphous metal and ceramic materials have been produced as gas-atomized powders and applied as near full density, nonporous coatings with the high-velocity oxy-fuel process. This article summarizes the performance of these coatings as corrosion-resistant barriers and as neutron absorbers. This article also presents a simple cost model to quantify the economic benefits possible with these new materials.

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.

Multi-Functions of Carbonated Calcium Deficient Hydroxyapatite (CDHA)

NASA Astrophysics Data System (ADS)

Zhou, Huan

Natural bone is a complex composite mainly constituted of inorganic minerals and organic collagen molecules. Calcium phosphate (CaP) based materials have been proposed as the predominant bone substitute for bone tissue engineering applications due to their chemical similarity to bone mineral. Amorphous carbonated calcium deficient hydroxyapatite (CDHA) is an important compound among CaP materials because of the amorphous crystallite structure. The presence of extra ions in its lattice structure not only influences cell attachment and proliferation of osteoblasts, but also helps in bone metabolism. Biomimetic coating approach is the most widely used approach to produce CDHA coatings to implant. It is a process using simulated body fluid (SBF) to deposit bone-like CDHA coating to various material surfaces. The CDHA formation mechanism, SBF compositions and reacting conditions of biomimetic coating have already been sufficiently studied and compared in the past 20 years. It is an attempt in this thesis to explore new applications of SBF in biomedical research, focusing on different biomaterial applications: 1) based on the low temperature reaction condition of SBF, bisphosphonate incorporated CDHA coatings were deposited onto Ti6Al4V surface for the treatment of osteoporosis; 2) amorphous calcium phosphate nanospheres with extra elements in the lattice structure were prepared by a novel microwave assisted approach, providing a new potential of CaP materials production; 3) CDHA particles formed in SBF can be used as great fillers with biopolymers for preparing biocomposites for biomedical applications; 4) based on the high activity of CDHA amorphous structure and the stabilization ability of ethanol, yttrium and europium doped calcium phosphates were prepared using CDHA as a sacrificing template. In the end, future work based on these observations in the thesis is addressed, including areas of drug delivery, biocomposite fabrication and preparation of functionalized calcium phosphate materials.

A model calculation of coherence effects in the elastic backscattering of very low energy electrons (1-20 eV) from amorphous ice.

PubMed

Liljequist, David

2012-01-01

Backscattering of very low energy electrons in thin layers of amorphous ice is known to provide experimental data for the elastic and inelastic cross sections and indicates values to be expected in liquid water. The extraction of cross sections was based on a transport analysis consistent with Monte Carlo simulation of electron trajectories. However, at electron energies below 20 eV, quantum coherence effects may be important and trajectory-based methods may be in significant error. This possibility is here investigated by calculating quantum multiple elastic scattering of electrons in a simple model of a very small, thin foil of amorphous ice. The average quantum multiple elastic scattering of electrons is calculated for a large number of simulated foils, using a point-scatterer model for the water molecule and taking inelastic absorption into account. The calculation is compared with a corresponding trajectory simulation. The difference between average quantum scattering and trajectory simulation at energies below about 20 eV is large, in particular in the forward scattering direction, and is found to be almost entirely due to coherence effects associated with the short-range order in the amorphous ice. For electrons backscattered at the experimental detection angle (45° relative to the surface normal) the difference is however small except at electron energies below about 10 eV. Although coherence effects are in general found to be strong, the mean free path values derived by trajectory-based analysis may actually be in fair agreement with the result of an analysis based on quantum scattering, at least for electron energies larger than about 10 eV.

Formation of polycrystalline MgB2 synthesized by powder in sealed tube method with different initial boron phase

NASA Astrophysics Data System (ADS)

Yudanto, Sigit Dwi; Imaduddin, Agung; Kurniawan, Budhy; Manaf, Azwar

2018-04-01

Magnesium diboride, MgB2 is a new high critical temperature superconductor that discovered in the beginning of the 21st century. The MgB2 has a simple crystal structure and a high critical temperature, which can be manufactured in several forms like thin films, tapes, wires including bulk in the large scale. For that reason, the MgB2 has good prospects for various applications in the field of electronic devices. In the current work, we have explored the synthesis of MgB2 polycrystalline using powder in a sealed tube method. Different initial boron phase for the synthesized of MgB2 polycrystalline were used. These were, in addition to magnesium powders, crystalline boron, amorphous boron and combination both of them were respectively fitted in the synthesis. The raw materials were mixed in a stoichiometric ratio of Mg: B=1:2, ground using agate mortar, packed into stainless steel SS304. The pack was then sintered at temperature of 800°C for 2 hours in air atmosphere. Phase formation of MgB2 polycrystalline in difference of initial boron phase was characterized using XRD and SEM. Referring to the diffraction pattern and microstructure observation, MgB2 polycrystalline was formed, and the formation was effective when using the crystalline Mg and fully amorphous B as the raw materials. The critical temperature of the specimen was evaluated by the cryogenic magnet. The transition temperature of the MgB2 specimen synthesized using crystalline magnesium and full amorphous boron is 42.678 K (ΔTc = 0.877 K).

Investigating the Impact of Drug Crystallinity in Amorphous Tacrolimus Capsules on Pharmacokinetics and Bioequivalence Using Discriminatory In Vitro Dissolution Testing and Physiologically Based Pharmacokinetic Modeling and Simulation.

PubMed

Purohit, Hitesh S; Trasi, Niraj S; Sun, Dajun D; Chow, Edwin C Y; Wen, Hong; Zhang, Xinyuan; Gao, Yi; Taylor, Lynne S

2018-05-01

Delivering a drug in amorphous form in a formulated product is a strategy used to enhance the apparent solubility of a drug substance and its oral bioavailability. Drug crystallization in such products may occur during the manufacturing process or on storage, reducing the solubility advantage of the amorphous drug. However, the impact of partial drug crystallization in the drug product on the resulting bioavailability and pharmacokinetics is unknown. In this study, dissolution testing of commercial tacrolimus capsules (which are formulated to contain amorphous drug), both fresh and those containing different amounts of crystalline drug, was conducted using both United States Pharmacopeia and noncompendial dissolution tests with different dissolution media and volumes. A physiologically based pharmacokinetic (PBPK) absorption model was developed to predict the impact of crystallinity extent on the oral absorption of the products and to evaluate the discriminatory ability of the different dissolution methods. Virtual bioequivalence simulations between partially crystallized tacrolimus capsules versus fresh Prograf or generic tacrolimus capsules were performed using the PBPK model and in vitro dissolution data of the various fresh and partially crystallized capsules under United States Pharmacopeia and noncompendial dissolution conditions. The results suggest that compendial dissolution tests may not be sufficiently discriminatory with respect to the presence of crystallinity in an amorphous formulation. Nonsink dissolution tests using lower dissolution volumes generate more discriminatory profiles that predict different pharmacokinetics of tacrolimus capsules containing different extents of drug crystallinity. In conclusion, the PBPK modeling approach can be used to assess the impact of partial drug crystallinity in the formulated product and to guide the development of appropriate dissolution methods. Copyright © 2018 American Pharmacists Association®. All rights reserved.

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.

Hierarchical structure and physicochemical properties of plasticized chitosan.

PubMed

Meng, Qingkai; Heuzey, Marie-Claude; Carreau, Pierre J

2014-04-14

Plasticized chitosan with hierarchical structure, including multiple length scale structural units, was prepared by a "melt"-based method, that is, thermomechanical mixing, as opposed to the usual casting-evaporation procedure. Chitosan was successfully plasticized by thermomechanical mixing in the presence of concentrated lactic acid and glycerol using a batch mixer. Different plasticization formulations were compared in this study, in which concentrated lactic acid was used as protonation agent as well as plasticizer. The microstructure of thermomechanically plasticized chitosan was investigated by X-ray diffraction, scanning electron microscopy, and optical microscopy. With increasing amount of additional plasticizers (glycerol or water), the crystallinity of the plasticized chitosan decreased from 63.7% for the original chitosan powder to almost zero for the sample plasticized with additional water. Salt linkage between lactic acid molecules and amino side chains of chitosan was confirmed by FTIR spectroscopy: the lactic acid molecules expanded the space between the chitosan molecules of the crystalline phase. In the presence of other plasticizers (glycerol and water), various levels of structural units including an amorphous phase, nanofibrils, nanofibril clusters, and microfibers were produced under mechanical shear and thermal energy and identified for the first time. The thermal and thermomechanical properties of the plasticized chitosan were measured by thermogravimetric analysis, differential scanning calorimetric, and DMA. These properties were correlated with the different levels of microstructure, including multiple structural units.

Single-implant overdentures retained by the Novaloc attachment system: study protocol for a mixed-methods randomized cross-over trial.

PubMed

de Souza, Raphael F; Bedos, Christophe; Esfandiari, Shahrokh; Makhoul, Nicholas M; Dagdeviren, Didem; Abi Nader, Samer; Jabbar, Areej A; Feine, Jocelyne S

2018-04-23

Overdentures retained by a single implant in the midline have arisen as a minimal implant treatment for edentulous mandibles. The success of this treatment depends on the performance of a single stud attachment that is susceptible to wear-related retention loss. Recently developed biomaterials used in attachments may result in better performance of the overdentures, offering minimal retention loss and greater patient satisfaction. These biomaterials include resistant polymeric matrixes and amorphous diamond-like carbon applied on metallic components. The objective of this explanatory mixed-methods study is to compare Novaloc, a novel attachment system with such characteristics, to a traditional alternative for single implants in the mandible of edentate elderly patients. We will carry out a randomized cross-over clinical trial comparing Novaloc attachments to Locators for single-implant mandibular overdentures in edentate elderly individuals. Participants will be followed for three months with each attachment type; patient-based, clinical, and economic outcomes will be gathered. A sample of 26 participants is estimated to be required to detect clinically relevant differences in terms of the primary outcome (patient ratings of general satisfaction). Participants will choose which attachment they wish to keep, then be interviewed about their experiences and preferences with a single implant prosthesis and with the two attachments. Data from the quantitative and qualitative assessments will be integrated through a mixed-methods explanatory strategy. A last quantitative assessment will take place after 12 months with the preferred attachment; this latter assessment will enable measurement of the attachments' long-term wear and maintenance requirements. Our results will lead to evidence-based recommendations regarding these systems, guiding providers and patients when making decisions on which attachment systems and implant numbers will be most appropriate for individual cases. The recommendation of a specific attachment for elderly edentulous patients may combine positive outcomes from patient perspectives with low cost, good maintenance, and minimal invasiveness. ClinicalTrials.gov, NCT03126942 . Registered on 13 April 2017.

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.

Application of amorphous carbon based materials as antireflective coatings on crystalline silicon solar cells

NASA Astrophysics Data System (ADS)

da Silva, D. S.; Côrtes, A. D. S.; Oliveira, M. H.; Motta, E. F.; Viana, G. A.; Mei, P. R.; Marques, F. C.

2011-08-01

We report on the investigation of the potential application of different forms of amorphous carbon (a-C and a-C:H) as an antireflective coating for crystalline silicon solar cells. Polymeric-like carbon (PLC) and hydrogenated diamond-like carbon films were deposited by plasma enhanced chemical vapor deposition. Tetrahedral amorphous carbon (ta-C) was deposited by the filtered cathodic vacuum arc technique. Those three different amorphous carbon structures were individually applied as single antireflective coatings on conventional (polished and texturized) p-n junction crystalline silicon solar cells. Due to their optical properties, good results were also obtained for double-layer antireflective coatings based on PLC or ta-C films combined with different materials. The results are compared with a conventional tin dioxide (SnO2) single-layer antireflective coating and zinc sulfide/magnesium fluoride (ZnS/MgF2) double-layer antireflective coatings. An increase of 23.7% in the short-circuit current density, Jsc, was obtained using PLC as an antireflective coating and 31.7% was achieved using a double-layer of PLC with a layer of magnesium fluoride (MgF2). An additional increase of 10.8% was obtained in texturized silicon, representing a total increase (texturization + double-layer) of about 40% in the short-circuit current density. The potential use of these materials are critically addressed considering their refractive index, optical bandgap, absorption coefficient, hardness, chemical inertness, and mechanical stability.

Phonon-interface scattering in multilayer graphene on an amorphous support

PubMed Central

Sadeghi, Mir Mohammad; Jo, Insun; Shi, Li

2013-01-01

The recent studies of thermal transport in suspended, supported, and encased graphene just began to uncover the richness of two-dimensional phonon physics, which is relevant to the performance and reliability of graphene-based functional materials and devices. Among the outstanding questions are the exact causes of the suppressed basal-plane thermal conductivity measured in graphene in contact with an amorphous material, and the layer thickness needed for supported or embedded multilayer graphene (MLG) to recover the high thermal conductivity of graphite. Here we use sensitive in-plane thermal transport measurements of graphene samples on amorphous silicon dioxide to show that full recovery to the thermal conductivity of the natural graphite source has yet to occur even after the MLG thickness is increased to 34 layers, considerably thicker than previously thought. This seemingly surprising finding is explained by long intrinsic scattering mean free paths of phonons in graphite along both basal-plane and cross-plane directions, as well as partially diffuse scattering of MLG phonons by the MLG-amorphous support interface, which is treated by an interface scattering model developed for highly anisotropic materials. Based on the phonon transmission coefficient calculated from reported experimental thermal interface conductance results, phonons emerging from the interface consist of a large component that is scattered across the interface, making rational choice of the support materials a potential approach to increasing the thermal conductivity of supported MLG. PMID:24067656

Investigation of the influence of pretreatment parameters on the surface characteristics of amorphous metal for use in power industry

NASA Astrophysics Data System (ADS)

Nieroda, Jolanta; Rybak, Andrzej; Kmita, Grzegorz; Sitarz, Maciej

2018-05-01

Metallic glasses are metallic materials, which exhibit an amorphous structure. These are mostly three or more component alloys, and some of them are magnetic metals. Materials of this kind are characterized by high electrical resistivity and at the same time exhibit very good magnetic properties (e.g. low-magnetization loss). The above mentioned properties are very useful in electrical engineering industry and this material is more and more popular as a substance for high-efficiency electrical devices production. This industry area is still evolving, and thus even higher efficiency of apparatus based on amorphous material is expected. A raw material must be carefully investigated and characterized before the main production process is started. Presented work contains results of complementary examination of amorphous metal Metglas 2605. Studies involve two ways to obtain clean and oxidized surface with high reactivity, namely degreasing followed by annealing process and plasma treatment. The amorphous metal parameters were examined by means of several techniques: surface free energy (SFE) measurements by sessile drop method, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and both ex situ and in situ Raman spectroscopy. Additionally, influence of plasma parameters on wetting properties were optimized in systematic way with Design of Experiments (DOE) method. A wide range of used methods allow to fully investigate the amorphous metal material during preliminary preparation of surface. Obtained results provide information about appropriate parameters that should be applied in order to obtain highly reactive surface with functional oxide layer on it.

Structure-Property Relationships in Amorphous Transparent Conducting Oxides

NASA Astrophysics Data System (ADS)

Moffitt, Stephanie Lucille

Over the last 20 years a new field of amorphous transparent conducting oxides (a-TCOs) has developed. The amorphous nature of these films makes them well suited for large area applications. In addition, a-TCOs can be made at low temperatures and through solution processing methods. These assets provide promising opportunities to improve applications such as solar cells and back-lit displays where traditional crystalline TCOs are used. In addition, it opens the door for new technological applications including the possibility for transparent, flexible electronics. Despite the recent growth in this field, fundamental understanding of the true nature of conductivity and the amorphous structure in this materials system is still progressing. To develop a greater understanding of a-TCOs, structure-property relationships were developed in the a-IGO and a-IZO systems. From the combination of element-specific local structure studies and liquid quench molecular dynamics simulations it is clear that a degree of structure remains in a-TCOs. By understanding this structure, the effect of gallium on thermal stability, carrier concentration and carrier mobility is understood. The source of charge carriers in a-IZO is identified as oxygen vacancies through the application of in situ Brouwer analysis. The continued development of the Brouwer analysis technique for use in amorphous oxides adds to the available methods for studying defects in amorphous systems. Finally, the foundational knowledge gained from the in-depth study of a-IGO was extended to understand the role of combustion processing and pulsed laser deposition as growth methods for transistors based on a-IGO.

Simulation and experimental analysis of nanoindentation and mechanical properties of amorphous NiAl alloys.

PubMed

Wang, Chih-Hao; Fang, Te-Hua; Cheng, Po-Chien; Chiang, Chia-Chin; Chao, Kuan-Chi

2015-06-01

This paper used numerical and experimental methods to investigate the mechanical properties of amorphous NiAl alloys during the nanoindentation process. A simulation was performed using the many-body tight-binding potential method. Temperature, plastic deformation, elastic recovery, and hardness were evaluated. The experimental method was based on nanoindentation measurements, allowing a precise prediction of Young's modulus and hardness values for comparison with the simulation results. The indentation simulation results showed a significant increase of NiAl hardness and elastic recovery with increasing Ni content. Furthermore, the results showed that hardness and Young's modulus increase with increasing Ni content. The simulation results are in good agreement with the experimental results. Adhesion test of amorphous NiAl alloys at room temperature is also described in this study.

Electrically Active Defects In Solar Cells Based On Amorphous Silicon/Crystalline Silicon Heterojunction After Irradiation By Heavy Xe Ions

NASA Astrophysics Data System (ADS)

Harmatha, Ladislav; Mikolášek, Miroslav; Stuchlíková, L'ubica; Kósa, Arpád; Žiška, Milan; Hrubčín, Ladislav; Skuratov, Vladimir A.

2015-11-01

The contribution is focused on the diagnostics of structures with a heterojunction between amorphous and crystalline silicon prepared by HIT (Heterojunction with an Intrinsic Thin layer) technology. The samples were irradiated by Xe ions with energy 167 MeV and doses from 5 × 108 cm-2 to 5 × 1010 cm-2. Radiation defects induced in the bulk of Si and at the hydrogenated amorphous silicon and crystalline silicon (a-Si:H/c-Si) interface were identified by Deep Level Transient Spectroscopy (DLTS). Radiation induced A-centre traps, boron vacancy traps and different types of divacancies with a high value of activation energy were observed. With an increased fluence of heavy ions the nature and density of the radiation induced defects was changed.

High resistivity iron-based, thermally stable magnetic material for on-chip integrated inductors

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

Deligianni, Hariklia; Gallagher, William J.; Mason, Maurice

An on-chip magnetic structure includes a palladium activated seed layer and a substantially amorphous magnetic material disposed onto the palladium activated seed layer. The substantially amorphous magnetic material includes nickel in a range from about 50 to about 80 atomic % (at. %) based on the total number of atoms of the magnetic material, iron in a range from about 10 to about 50 at. % based on the total number of atoms of the magnetic material, and phosphorous in a range from about 0.1 to about 30 at. % based on the total number of atoms of the magneticmore » material. The magnetic material can include boron in a range from about 0.1 to about 5 at. % based on the total number of atoms of the magnetic material.« less

Friction and surface chemistry of some ferrous-base metallic glasses

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

The friction properties of some ferrous-base metallic glasses were measured both in argon and in vacuum to a temperature of 350 C. The alloy surfaces were also analyzed with X-ray photoelectron spectroscopy to identify the compounds and elements present on the surface. The results of the investigation indicate that even when the surfaces of the amorphous alloys, or metallic glasses, are atomically clean, bulk contaminants such as boric oxide and silicon dioxide diffuse to the surfaces. Friction measurements in both argon and vacuum indicate that the alloys exhibit higher coefficients of friction in the crystalline state than they do in the amorphous state.

Safe gas handling and system design for the large scale production of amorphous silicon based solar cells

NASA Astrophysics Data System (ADS)

Fortmann, C. M.; Farley, M. V.; Smoot, M. A.; Fieselmann, B. F.

1988-07-01

Solarex is one of the leaders in amorphous silicon based photovoltaic production and research. The large scale production environment presents unique safety concerns related to the quantity of dangerous materials as well as the number of personnel handling these materials. The safety measures explored by this work include gas detection systems, training, and failure resistant gas handling systems. Our experiences with flow restricting orifices in the CGA connections and the use of steel cylinders is reviewed. The hazards and efficiency of wet scrubbers for silane exhausts are examined. We have found it to be useful to provide the scrubbler with temperature alarms.

Conditions for a carrier multiplication in amorphous-selenium based photodetector

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

Masuzawa, Tomoaki; Kuniyoshi, Shingo; Onishi, Masanori

2013-02-18

Amorphous selenium is a promising candidate for high sensitivity photodetector due to its unique carrier multiplication phenomenon. More than 10 carriers can be generated per incident photon, which leads to high photo-conversion efficiency of 1000% that allows real-time imaging in dark ambient. However, application of this effect has been limited to specific devices due to the lack in material characterization. In this article, mechanism of carrier multiplication has been clarified using time-of-flight secondary ion mass spectroscopy and Raman spectroscopy. A prototype photodetector achieved photo conversion efficiency of 4000%, which explains the signal enhancement mechanism in a-Se based photodetector.

Effect of Al2O3 insulator thickness on the structural integrity of amorphous indium-gallium-zinc-oxide based thin film transistors.

PubMed

Kim, Hak-Jun; Hwang, In-Ju; Kim, Youn-Jea

2014-12-01

The current transparent oxide semiconductors (TOSs) technology provides flexibility and high performance. In this study, multi-stack nano-layers of TOSs were designed for three-dimensional analysis of amorphous indium-gallium-zinc-oxide (a-IGZO) based thin film transistors (TFTs). In particular, the effects of torsional and compressive stresses on the nano-sized active layers such as the a-IGZO layer were investigated. Numerical simulations were carried out to investigate the structural integrity of a-IGZO based TFTs with three different thicknesses of the aluminum oxide (Al2O3) insulator (δ = 10, 20, and 30 nm), respectively, using a commercial code, COMSOL Multiphysics. The results are graphically depicted for operating conditions.

Development of an Amorphous Selenium-Based Photodetector Driven by a Diamond Cold Cathode

PubMed Central

Masuzawa, Tomoaki; Saito, Ichitaro; Yamada, Takatoshi; Onishi, Masanori; Yamaguchi, Hisato; Suzuki, Yu; Oonuki, Kousuke; Kato, Nanako; Ogawa, Shuichi; Takakuwa, Yuji; Koh, Angel T. T.; Chua, Daniel H. C.; Mori, Yusuke; Shimosawa, Tatsuo; Okano, Ken

2013-01-01

Amorphous-selenium (a-Se) based photodetectors are promising candidates for imaging devices, due to their high spatial resolution and response speed, as well as extremely high sensitivity enhanced by an internal carrier multiplication. In addition, a-Se is reported to show sensitivity against wide variety of wavelengths, including visible, UV and X-ray, where a-Se based flat-panel X-ray detector was proposed. In order to develop an ultra high-sensitivity photodetector with a wide detectable wavelength range, a photodetector was fabricated using a-Se photoconductor and a nitrogen-doped diamond cold cathode. In the study, a prototype photodetector has been developed, and its response to visible and ultraviolet light are characterized. PMID:24152932

Radiation damage and nanocrystal formation in uranium-niobium titanates

NASA Astrophysics Data System (ADS)

Lian, J.; Wang, S. X.; Wang, L. M.; Ewing, R. C.

2001-07-01

Two uranium-niobium titanates, U 2.25Nb 1.90Ti 0.32O 9.8 and Nb 2.75U 1.20Ti 0.36O 10, formed during the synthesis of brannnerite (UTi 2O 6), a minor phase in titanate-based ceramics investigated for plutonium immobilization. These uranium titanates were subjected to 800 keV Kr 2+ irradiation from 30 to 973 K. The critical amorphization dose of the U-rich and Nb-rich titanates at room temperature were 4.72×10 17 and 5×10 17 ions/ m2, respectively. At elevated temperature, the critical amorphization dose increases due to dynamic thermal annealing. The critical amorphization temperature for both Nb-rich and U-rich titanates is ˜933 K under a 800 keV Kr 2+ irradiation. Above the critical amorphization temperature, nanocrystals with an average size of ˜15 nm were observed. The formation of nanocrystals is due to epitaxial recrystallization. At higher temperatures, an ion irradiation-induced nucleation-growth mechanism also contributes to the formation of nanocrystals.

Plasma plume effects on the conductivity of amorphous-LaAlO{sub 3}/SrTiO{sub 3} interfaces grown by pulsed laser deposition in O{sub 2} and Ar

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

Sambri, A.; Amoruso, S.; Bruzzese, R.

2012-06-04

Amorphous-LaAlO{sub 3}/SrTiO{sub 3} interfaces exhibit metallic conductivity similar to those found for the extensively studied crystalline-LaAlO{sub 3}/SrTiO{sub 3} interfaces. Here, we investigate the conductivity of the amorphous-LaAlO{sub 3}/SrTiO{sub 3} interfaces grown in different pressures of O{sub 2} and Ar background gases. During the deposition, the LaAlO{sub 3} ablation plume is also studied, in situ, by fast photography and space-resolved optical emission spectroscopy. An interesting correlation between interfacial conductivity and kinetic energy of the Al atoms in the plume is observed: to assure conducting interfaces of amorphous-LaAlO{sub 3}/SrTiO{sub 3}, the kinetic energy of Al should be higher than 1 eV. Ourmore » findings add further insights on mechanisms leading to interfacial conductivity in SrTiO{sub 3}-based oxide heterostructures.« less

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

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

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.

Charge collection microscopy of in-situ switchable PRAM line cells in a scanning electron microscope: Technique development and unique observations

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

Oosthoek, J. L. M.; Schuitema, R. W.; Brink, G. H. ten

2015-03-15

An imaging method has been developed based on charge collection in a scanning electron microscope (SEM) that allows discrimination between the amorphous and crystalline states of Phase-change Random Access Memory (PRAM) line cells. During imaging, the cells are electrically connected and can be switched between the states and the resistance can be measured. This allows for electrical characterization of the line cells in-situ in the SEM. Details on sample and measurement system requirements are provided which turned out to be crucial for the successful development of this method. Results show that the amorphous or crystalline state of the line cellsmore » can be readily discerned, but the spatial resolution is relatively poor. Nevertheless, it is still possible to estimate the length of the amorphous mark, and also for the first time, we could directly observe the shift of the amorphous mark from one side of the line cell to the other side when the polarity of the applied (50 ns) RESET pulse was reversed.« less

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

ANSYS-Based Simulation and Optimization on Temperature Field of Amorphous Ingot Made by Water Quenching

NASA Astrophysics Data System (ADS)

Zhao, W.; Sun, Z.; Tang, Z.; Liaw, P. K.; Li, J.; Liu, R. P.; Li, Gong

2014-05-01

2D finite element analysis was conducted on the temperature field to create an amorphous ingot by vacuum water quenching. An optimized analysis document was then written by ANSYS parametric design language, and the optimal design modules of ANSYS were used to study the inside diameter and wall thickness of the quartz tube, as well as the water temperature. The microstructure and the phase structure of the amorphous ingot were evaluated by scanning electron microscopy and X-ray diffraction, respectively. Results show that during the cooling process, the thinner wall thickness, smaller diameter of the ingot, or lower temperature of the water environment can result in higher cooling rate at a given temperature. Besides, the gap between the different cooling rates induced by wall thickness or diameter of the ingot narrows down as the temperature decreases, and the gap between the different cooling rates induced by temperature of the water environment remains constant. The process parameters in creating an amorphous ingot, which is optimized by the finite element analysis on the temperature field, are reliable.

Subnanometer Cobalt-Hydroxide-Anchored N-Doped Carbon Nanotube Forest for Bifunctional Oxygen Catalyst.

PubMed

Kim, Ji Eun; Lim, Joonwon; Lee, Gil Yong; Choi, Sun Hee; Maiti, Uday Narayan; Lee, Won Jun; Lee, Ho Jin; Kim, Sang Ouk

2016-01-27

Electrochemical oxygen redox reactions are the crucial elements for energy conversion and storage including fuel cells and metal air batteries. Despite tremendous research efforts, developing high-efficient, low-cost, and durable bifunctional oxygen catalysts remains a major challenge. We report a new class of hybrid material consisting of subnanometer thick amorphous cobalt hydroxide anchored on NCNT as a durable ORR/OER bifunctional catalyst. Although amorphous cobalt species-based catalysts are known as good OER catalysts, hybridizing with NCNT successfully enhanced ORR activity by promoting a 4e reduction pathway. Abundant charge carriers in amorphous cobalt hydroxide are found to trigger the superior OER activity with high current density and low Tafel slope as low as 36 mV/decade. A remarkably high OER turnover frequency (TOF) of 2.3 s(-1) at an overpotential of 300 mV was obtained, one of the highest values reported so far. Moreover, the catalytic activity was maintained over 120 h of cycling. The unique subnanometer scale morphology of amorphous hydroxide cobalt species along with intimate cobalt species-NCNT interaction minimizes the deactivation of catalyst during prolonged repeated cycles.

Solvothermal synthesis of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanophosphor in water/diethylene glycol system

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

Takeshita, Satoru; Honda, Joji; Isobe, Tetsuhiko, E-mail: isobe@applc.keio.ac.jp

2012-05-15

The influence of aging of the suspension containing the amorphous precusors on structural, compositional and photoluminescent properties is studied to understand the mechanism on the formation of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanoparticles during the solvothermal reaction in the water/diethylene glycol mixed solvent. Aging at 200 Degree-Sign C for 20 min forms the crystalline Zn{sub 2}GeO{sub 4} nanorods and then they grow up to {approx} 50 nm in mean length after aging for 240 min. Their interplanar spacing of (410) increases with increasing the aging time. The photoluminescence intensity corresponding to the d-d transition of Mn{sup 2+} increases with increasing themore » aging time up to 120 min, and then decreases after aging for 240 min. The photoluminescence lifetime decreases with increasing the aging time, indicating the locally concentrated Mn{sup 2+} ions. These results reveal that Mn{sup 2+} ions gradually replace Zn{sup 2+} ions near surface through repeating dissolusion and precipitation processes during prolonged aging after the complete crystallization of Zn{sub 2}GeO{sub 4}. - Graphical abstract: TEM images of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanoparticles aged at 200 Degree-Sign C for different aging times in the mixed solvent of water and diethylene glycol. Highlights: Black-Right-Pointing-Pointer Mechanism on formation of Zn{sub 2}GeO{sub 4}:Mn{sup 2+} nanophosphor under solvothermal condition. Black-Right-Pointing-Pointer Zn{sub 2}GeO{sub 4} nanorods crystallize via amorphous precursors. Black-Right-Pointing-Pointer Gradual substitution of Mn{sup 2+} during prolonged aging. Black-Right-Pointing-Pointer Such an inhomogeneous Mn{sup 2+} doping process results in concentration quenching.« less

Novel injectable, self-gelling hydrogel-microparticle composites for bone regeneration consisting of gellan gum and calcium and magnesium carbonate microparticles.

PubMed

Douglas, Timothy E L; Łapa, Agata; Reczyńska, Katarzyna; Krok-Borkowicz, Małgorzata; Pietryga, Krzysztof; Samal, Sangram Keshari; Declercq, Heidi A; Schaubroeck, David; Boone, Marijn; Van der Voort, Pascal; De Schamphelaere, Karel; Stevens, Christian V; Bliznuk, Vitaliy; Balcaen, Lieve; Parakhonskiy, Bogdan V; Vanhaecke, Frank; Cnudde, Veerle; Pamuła, Elżbieta; Skirtach, Andre G

2016-11-21

The suitability of hydrogel biomaterials for bone regeneration can be improved by incorporation of an inorganic phase in particle form, thus maintaining hydrogel injectability. In this study, carbonate microparticles containing different amounts of calcium (Ca) and magnesium (Mg) were added to solutions of the anionic polysaccharide gellan gum (GG) to crosslink GG by release of Ca 2+ and Mg 2+ from microparticles and thereby induce formation of hydrogel-microparticle composites. It was hypothesized that increasing Mg content of microparticles would promote GG hydrogel formation. The effect of Mg incorporation on cytocompatibility and cell growth was also studied. Microparticles were formed by mixing Ca 2+ and Mg 2+ and [Formula: see text] ions in varying concentrations. Microparticles were characterized physiochemically and subsequently mixed with GG solution to form hydrogel-microparticle composites. The elemental Ca:Mg ratio in the mineral formed was similar to the Ca:Mg ratio of the ions added. In the absence of Mg, vaterite was formed. At low Mg content, magnesian calcite was formed. Increasing the Mg content further caused formation of amorphous mineral. Microparticles of vaterite and magnesium calcite did not induce GG hydrogel formation, but addition of Mg-richer amorphous microparticles induced gelation within 20 min. Microparticles were dispersed homogeneously in hydrogels. MG-63 osteoblast-like cells were cultured in eluate from hydrogel-microparticle composites and on the composites themselves. All composites were cytocompatible. Cell growth was highest on composites containing particles with an equimolar Ca:Mg ratio. In summary, carbonate microparticles containing a sufficient amount of Mg induced GG hydrogel formation, resulting in injectable, cytocompatible hydrogel-microparticle composites.

From Interstellar Polycyclic Aromatic Hydrocarbons and Ice to the Origin of Life

NASA Technical Reports Server (NTRS)

Allamandola, Louis

2004-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In the dense ISM, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. The first part of this talk will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, abundances, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the presolar nebula, the materials frozen into the interstellar/precometary ices are photoprocessed by ultraviolet light and produce more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex materials on the early Earth and their composition may be related to the origin of life.

Shock-wave propagation and reflection in semicrystalline polyethylene: A molecular-level investigation

NASA Astrophysics Data System (ADS)

Elder, Robert M.; O'Connor, Thomas C.; Chantawansri, Tanya L.; Sliozberg, Yelena R.; Sirk, Timothy W.; Yeh, In-Chul; Robbins, Mark O.; Andzelm, Jan W.

2017-09-01

Semicrystalline polyethylene (PE) is attractive for a variety of mechanically demanding applications, where shock compression can occur. Although often highly crystalline, PE invariably contains nanoscale amorphous domains that influence shock propagation. Our objective in this work is to study the effects of such domains. To this end, we adopt a novel approach wherein we parametrize a simple continuum-level theory based on the shock impedance from molecular dynamics (MD) simulations. Using this theory, we predict how crystalline/amorphous interfaces attenuate shocks via energy reflection due to the impedance mismatch between the phases. The theory predicts that these interfaces attenuate weak shocks more effectively than strong shocks. We compare the theory to explicit nonequilibrium MD simulations of compressive shocks in semicrystalline PE containing nanometer-scale amorphous regions of varying size, where we analyze the pressure response and reflection of energy. The theory and simulations show good agreement for strong shocks (≥1.0 km /s ), but for weak shocks (<1.0 km /s ) the simulations show enhanced energy reflection relative to the continuum predictions. Furthermore, the simulations show an effect not captured by the continuum theory: the size of amorphous regions is important. The theory assumes a sharp (discontinuous) interface between two bulk phases and a sharp change in thermodynamic and hydrodynamic quantities at the shock front. However, the simulations show that when amorphous domains are narrow—with widths comparable to the shock front—reflection is reduced compared to the predictions. We identify several nanoscale mechanisms that reduce the impedance mismatch, and thus reduce reflection, at thin amorphous domains. First, the two-wave elastic-plastic structure of shocks in crystalline PE allows the faster-moving elastic precursor wave to compress small amorphous domains before the plastic wave arrives. Second, confinement between stiff, ordered crystalline domains increases the stiffness and chain ordering in small amorphous regions. Moreover, in terms of stiffness the interfaces are similar in width to the shock front, which may contribute to the underprediction of the theory for weak shocks, where the shock front is widest. We conclude by discussing the significance of these results, namely, how they can be applied to tune shock attenuation for particular applications.

Dentine Tubule Occlusion by Novel Bioactive Glass-Based Toothpastes

PubMed Central

Hill, Robert G.; Chen, Xiaojing

2018-01-01

There are numerous over-the-counter (OTC) and professionally applied (in-office) products and techniques currently available for the treatment of dentine hypersensitivity (DH), but more recently, the use of bioactive glasses in toothpaste formulations have been advocated as a possible solution to managing DH. Aim. The aim of the present study, therefore, was to compare several bioactive glass formulations to investigate their effectiveness in an established in vitro model. Materials and Methods. A 45S5 glass was synthesized in the laboratory together with several other glass formulations: (1) a mixed glass (fluoride and chloride), (2) BioMinF, (3) a chloride glass, and (4) an amorphous chloride glass. The glass powders were formulated into five different toothpaste formulations. Dentine discs were sectioned from extracted human teeth and prepared for the investigation by removing the cutting debris (smear layer) following sectioning using a 6% citric acid solution for 2 minutes. Each disc was halved to provide test and control halves for comparison following the brushing of the five toothpaste formulations onto the test halves for each toothpaste group. Following the toothpaste application, the test discs were immersed in either artificial saliva or exposed to an acid challenge. Results. The dentine samples were analyzed using scanning electron microscopy (SEM), and observation of the SEM images indicated that there was good surface coverage following artificial saliva immersion. Furthermore, although the acid challenge removed the hydroxyapatite layer on the dentine surface for most of the samples, except for the amorphous chloride glass, there was evidence of tubular occlusion in the dentine tubules. Conclusions. The conclusions from the study would suggest that the inclusion of bioactive glass into a toothpaste formulation may be an effective approach to treat DH. PMID:29849637

The Majorana Low-noise Low-background Front-end Electronics

NASA Astrophysics Data System (ADS)

Abgrall, N.; Aguayo, E.; Avignone, F. T.; Barabash, A. S.; Bertrand, F. E.; Boswell, M.; Brudanin, V.; Busch, M.; Byram, D.; Caldwell, A. S.; Chan, Y.-D.; Christofferson, C. D.; Combs, D. C.; Cuesta, C.; Detwiler, J. A.; Doe, P. J.; Efremenko, Yu.; Egorov, V.; Ejiri, H.; Elliott, S. R.; Fast, J. E.; Finnerty, P.; Fraenkle, F. M.; Galindo-Uribarri, A.; Giovanetti, G. K.; Goett, J.; Green, M. P.; Gruszko, J.; Guiseppe, V. E.; Gusev, K.; Hallin, A. L.; Hazama, R.; Hegai, A.; Henning, R.; Hoppe, E. W.; Howard, S.; Howe, M. A.; Keeter, K. J.; Kidd, M. F.; Kochetov, O.; Konovalov, S. I.; Kouzes, R. T.; LaFerriere, B. D.; Leon, J.; Leviner, L. E.; Loach, J. C.; MacMullin, J.; MacMullin, S.; Martin, R. D.; Meijer, S.; Mertens, S.; Nomachi, M.; Orrell, J. L.; O'Shaughnessy, C.; Overman, N. R.; Phillips, D. G.; Poon, A. W. P.; Pushkin, K.; Radford, D. C.; Rager, J.; Rielage, K.; Robertson, R. G. H.; Romero-Romero, E.; Ronquest, M. C.; Schubert, A. G.; Shanks, B.; Shima, T.; Shirchenko, M.; Snavely, K. J.; Snyder, N.; Suriano, A. M.; Thompson, J.; Timkin, V.; Tornow, W.; Trimble, J. E.; Varner, R. L.; Vasilyev, S.; Vetter, K.; Vorren, K.; White, B. R.; Wilkerson, J. F.; Wiseman, C.; Xu, W.; Yakushev, E.; Young, A. R.; Yu, C.-H.; Yumatov, V.

The MAJORANA DEMONSTRATOR will search for the neutrinoless double beta decay (ββ(0ν)) of the isotope 76Ge with a mixed array of enriched and natural germanium detectors. In view of the next generation of tonne-scale germanium-based ββ(0ν)-decay searches, a major goal of the MAJORANA DEMONSTRATOR is to demonstrate a path forward to achieving a background rate at or below 1 cnt/(ROI-t-y) in the 4 keV region of interest (ROI) around the 2039-keV Q-value of the 76Ge ββ(0ν)-decay. Such a requirement on the background level significantly constrains the design of the readout electronics, which is further driven by noise and energy resolution performances. We present here the low-noise low- background front-end electronics developed for the low-capacitance p-type point contact (P-PC) germanium detectors of the MAJORANA DEMONSTRATOR. This resistive-feedback front-end, specifically designed to have low mass, is fabricated on a radioassayed fused-silica substrate where the feedback resistor consists of a sputtered thin film of high purity amorphous germanium and the feedback capacitor is based on the capacitance between gold conductive traces.

Angle selective backscattered electron contrast in the low-voltage scanning electron microscope: Simulation and experiment for polymers.

PubMed

Wan, Q; Masters, R C; Lidzey, D; Abrams, K J; Dapor, M; Plenderleith, R A; Rimmer, S; Claeyssens, F; Rodenburg, C

2016-12-01

Recently developed detectors can deliver high resolution and high contrast images of nanostructured carbon based materials in low voltage scanning electron microscopes (LVSEM) with beam deceleration. Monte Carlo Simulations are also used to predict under which exact imaging conditions purely compositional contrast can be obtained and optimised. This allows the prediction of the electron signal intensity in angle selective conditions for back-scattered electron (BSE) imaging in LVSEM and compares it to experimental signals. Angle selective detection with a concentric back scattered (CBS) detector is considered in the model in the absence and presence of a deceleration field, respectively. The validity of the model prediction for both cases was tested experimentally for amorphous C and Cu and applied to complex nanostructured carbon based materials, namely a Poly(N-isopropylacrylamide)/Poly(ethylene glycol) Diacrylate (PNIPAM/PEGDA) semi-interpenetration network (IPN) and a Poly(3-hexylthiophene-2,5-diyl) (P3HT) film, to map nano-scale composition and crystallinity distribution by avoiding experimental imaging conditions that lead to a mixed topographical and compositional contrast. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

NASA Astrophysics Data System (ADS)

Benetti, Giulio; Cavaliere, Emanuele; Canteri, Adalberto; Landini, Giulia; Rossolini, Gian Maria; Pallecchi, Lucia; Chiodi, Mirco; Van Bael, Margriet J.; Winckelmans, Naomi; Bals, Sara; Gavioli, Luca

2017-03-01

Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

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

Abgrall, N.; Aguayo, Estanislao; Avignone, F. T.

The MAJORANA DEMONSTRATOR will search for the neutrinoless double beta decay (ββ(0ʋ) of the isotope 76Ge with a mixed array of enriched and natural Germanium detectors. In view of the next generation of tonne-scale germanium-based (ββ(0ʋ)-decay searches, a major goal of the MAJORANA DEMONSTRATOR is to demonstrate a path forward to achieving a background rate at or below 1 cnt/(ROI-t-y) in the 4 keV region of interest (ROI) around the 2039-keV Q-value of the 76Ge (ββ(0ʋ)-decay. Such a requirement on the background level significantly constrains the design of the readout electronics, which is further driven by noise and energy resolutionmore » performances. We present here the low-noise low background front-end electronics developed for the low-capacitance p-type point contact (P-PC) germanium detectors of the MAJORANA DEMONSTRATOR. This resistive-feedback front-end, specifically designed to have low mass, is fabricated on a radioassayed fused-silica substrate where the feedback resistor consists of a sputtered thin film of high purity amorphous germanium and the feedback capacitor is based on the capacitance between gold conductive traces.« less

The Majorana low-noise low-background front-end electronics

DOE PAGES

Abgrall, N.; Aguayo, E.; Avignone, III, F. T.; ...

2015-03-24

The Majorana Demonstrator will search for the neutrinoless double beta decay (ββ(0ν)) of the isotope ⁷⁶Ge with a mixed array of enriched and natural germanium detectors. In view of the next generation of tonne-scale germanium-based ββ(0ν)-decay searches, a major goal of the Majorana Demonstrator is to demonstrate a path forward to achieving a background rate at or below 1 cnt/(ROI-t-y) in the 4 keV region of interest (ROI) around the 2039-keV Q-value of the ⁷⁶Ge ββ(0ν)-decay. Such a requirement on the background level significantly constrains the design of the readout electronics, which is further driven by noise and energy resolutionmore » performances. We present here the low-noise low-background front-end electronics developed for the low-capacitance p-type point contact (P-PC) germanium detectors of the Majorana Demonstrator. This resistive-feedback front-end, specifically designed to have low mass, is fabricated on a radioassayed fused-silica substrate where the feedback resistor consists of a sputtered thin film of high purity amorphous germanium and the feedback capacitor is based on the capacitance between gold conductive traces.« less

Upper critical fields and superconducting transition temperatures of some zirconium-base amorphous transition-metal alloys

NASA Astrophysics Data System (ADS)

Karkut, M. G.; Hake, R. R.

1983-08-01

Superconducting upper critical fields Hc2(T), transition temperatures Tc and normal-state electrical resistivities ρn have been measured in the amorphous transition-metal alloy series Zr1-xCox, Zr1-xNix, (Zr1-xTix)0.78Ni0.22, and (Zr1-xNbx)0.78Ni0.22. Structural integrity of these melt-spun alloys is indicated by x-ray, density, bend-ductility, normal-state electrical resistivity, superconducting transition width, and mixed-state flux-pinning measurements. The specimens display Tc=2.1-3.8 K, ρn=159-190 μΩ cm, and |(dHc2dT)Tc|=28-36 kG/K. These imply electron mean free paths l~2-6 Å, zero-temperature Ginzburg-Landau coherence distances ξG0~50-70 Å, penetration depths λG0~(7-10)×103 Å, and extremely high dirtiness parameters ξ0l~300-1300. All alloys display Hc2(T) curves with negative curvature and (with two exceptions) fair agreement with the standard dirty-limit theory of Werthamer, Helfand, Hohenberg, and Maki (WHHM) for physically reasonable values of spin-orbit-coupling induced, electron-spin-flip scattering time τso. This is in contrast to the anomalously elevated Hc2(T) behavior which is nearly linear in T that is observed by some, and the unphysically low-τso fits to WHHM theory obtained by others, for various amorphous alloys. Current ideas that such anomalies may be due to alloy inhomogeneity are supported by present results on two specimens for which relatively low-τso fits of Hc2(T) to WHHM theory are coupled with superconductive evidence for inhomogeneity: relatively broad transitions at Tc and Hc2 current-density-dependent transitions at Hc2 and (in one specimen) a J-dependent, high-H (>Hc2), resistive "beak effect." In the Zr1-xCox and Zr1-xNix series, Tc decreases linearly with x (and with unfilled-shell average electron-to-atom ratio < ea > in the range 5.05<=< ea ><=6.40 in fair agreement with previous results for these systems and contrary to the Tc vs < ea > behavior of both amorphous and crystalline transition-metal alloys formed between near neighbors in the Periodic Table. Upper-critical-field and normal-state electrical resistivity measurements suggest that the molar electronic specific-heat coefficient γm decreases with x in parallel with Tc in the Zr1-xCox and Zr1-xNix series. In the equal-< ea > (Zr1-xTix)0.78Ni0.22 system, Tc decreases with x; in the (Zr1-xNbx)0.78Ni0.22 system, Tc first increases and then decreases with x (hence with < ea >). These diverse < ea > dependencies of Tc appear consistent with the ultraviolet-photoemission-spectroscopy indicated split-band model of such amorphous transition-metal alloys and the associated idea that the alloying dependence of Tc cannot be described by general Tc vs < ea > rules.

Near-infrared analysis of hydrogen-bonding in glass- and rubber-state amorphous saccharide solids.

PubMed

Izutsu, Ken-ichi; Hiyama, Yukio; Yomota, Chikako; Kawanishi, Toru

2009-01-01

Near-infrared (NIR) spectroscopic analysis of noncrystalline polyols and saccharides (e.g., glycerol, sorbitol, maltitol, glucose, sucrose, maltose) was performed at different temperatures (30-80 degrees C) to elucidate the effect of glass transition on molecular interaction. Transmission NIR spectra (4,000-12,000 cm(-1)) of the liquids and cooled-melt amorphous solids showed broad absorption bands that indicate random configuration of molecules. Heating of the samples decreased an intermolecular hydrogen-bonding OH vibration band intensity (6,200-6,500 cm(-1)) with a concomitant increase in a free and intramolecular hydrogen-bonding OH group band (6,600-7,100 cm(-1)). Large reduction of the intermolecular hydrogen-bonding band intensity at temperatures above the glass transition (T(g)) of the individual solids should explain the higher molecular mobility and lower viscosity in the rubber state. Mixing of the polyols with a high T(g) saccharide (maltose) or an inorganic salt (sodium tetraborate) shifted both the glass transition and the inflection point of the hydrogen-bonding band intensity to higher temperatures. The implications of these results for pharmaceutical formulation design and process monitoring (PAT) are discussed.

Production and Application of Olivine Nano-Silica in Concrete

NASA Astrophysics Data System (ADS)

Mardiana, Oesman; Haryadi

2017-05-01

The aim of this research was to produce nano silica by synthesis of nano silica through extraction and dissolution of ground olivine rock, and applied the nano silica in the design concrete mix. The producing process of amorphous silica used sulfuric acid as the dissolution reagent. The separation of ground olivine rock occurred when the rock was heated in a batch reactor containing sulfuric acid. The results showed that the optimum mole ratio of olivine- acid was 1: 8 wherein the weight ratio of the highest nano silica generated. The heating temperature and acid concentration influenced the mass of silica produced, that was at temperature of 90 °C and 3 M acid giving the highest yield of 44.90%. Characterization using Fourier Transform Infrared (FTIR ) concluded that amorphous silica at a wavenumber of 1089 cm-1 indicated the presence of siloxane, Si-O-Si, stretching bond. Characterization using Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) showed the surface and the size of the silica particles. The average size of silica particles was between 1-10 μm due to the rapid aggregation of the growing particles of nano silica into microparticles, caused of the pH control was not fully achieved.

Part-crystalline part-liquid state and rattling-like thermal damping in materials with chemical-bond hierarchy

DOE PAGES

Qiu, Wujie; Xi, Lili; Wei, Ping; ...

2014-10-06

Understanding thermal and phonon transport in solids has been of great importance in many disciplines such as thermoelectric materials, which usually requires an extremely low lattice thermal conductivity (LTC). Here, by analyzing the finite-temperature structural and vibrational characteristics of typical thermoelectric compounds such as filled skutterudites and Cu 3SbSe 3, we demonstrate a concept of part-crystalline part-liquid state in the compounds with chemical-bond hierarchy, in which certain constituent species weakly bond to other part of the crystal. Such a material could intrinsically manifest the coexistence of rigid crystalline sublattices and other fluctuating noncrystalline sublattices with thermally induced large-amplitude vibrations andmore » even flow of the group of species atoms, leading to atomic-level heterogeneity, mixed part-crystalline part-liquid structure, and thus rattling-like thermal damping due to the collective soft-mode vibrations similar to the Boson peak in amorphous materials. Lastly, the observed abnormal LTC close to the amorphous limit in these materials can only be described by an effective approach that approximately treats the rattling-like damping as a “resonant” phonon scattering.« less